WO2011134809A1 - Enzyme granules - Google Patents
Enzyme granules Download PDFInfo
- Publication number
- WO2011134809A1 WO2011134809A1 PCT/EP2011/056053 EP2011056053W WO2011134809A1 WO 2011134809 A1 WO2011134809 A1 WO 2011134809A1 EP 2011056053 W EP2011056053 W EP 2011056053W WO 2011134809 A1 WO2011134809 A1 WO 2011134809A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- core
- granule
- salt
- coating
- weight
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/105—Aliphatic or alicyclic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/142—Amino acids; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/163—Sugars; Polysaccharides
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/189—Enzymes
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K40/00—Shaping or working-up of animal feeding-stuffs
- A23K40/10—Shaping or working-up of animal feeding-stuffs by agglomeration; by granulation, e.g. making powders
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K40/00—Shaping or working-up of animal feeding-stuffs
- A23K40/30—Shaping or working-up of animal feeding-stuffs by encapsulating; by coating
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38609—Protease or amylase in solid compositions only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38672—Granulated or coated enzymes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
- C11D3/3953—Inorganic bleaching agents
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/98—Preparation of granular or free-flowing enzyme compositions
Definitions
- the present invention relates to granules comprising an enzyme-containing core surrounded by a protective coating and to their use in granular (or powder) detergents. More par- ticularly, it relates to enzyme granules with improved stability in powder detergents.
- Enzymes in the form of granules are commonly added to powder detergents, to improve the detergency. It is known in the art to incorporate enzymes into granules, to incorporate stabilizers into such granules and to surround the granules with a protective coating in order to protect the enzymes against inactivation caused by aggressive materials in the environment, e.g. to improve the storage stability of the enzyme when the granules are added to a granular detergent.
- coated enzyme granules are disclosed in WO 00/01793, WO 2004/003188 (US 2004/033927), WO 2004/067739, WO 99/32595, WO 2006/034710 (US 2006/073193) and WO 2007/044968.
- WO 99/37746 discloses a multi-layer detergent tablet.
- the invention provides a granule comprising a core and a protective coating, wherein:
- the core comprises an enzyme
- the core and/or the coating comprises a reducing agent or a peroxide decomposing catalyst or an antioxidant
- the core comprises a salt of a multivalent cation
- the core and/or the coating comprises an acidic buffer component
- the coating comprises a salt. Furthermore, the invention provides a surfactant and the granule.
- the core comprises the enzyme and the salt of a multivalent cation, and it may also comprise the reducing agent/antioxidant/peroxide decomposing catalyst and/or the acidic buffer component, typically as a homogenous blend.
- the blend may also include binders (such as synthetic polymer, wax, fat, or carbohydrate).
- the blend may further include additional materials such as fillers, fibre materials (cellulose or synthetic fibres), stabilizing agents, solubilising agents, suspension agents, viscosity regulating agents, light spheres, plasticizers, salts, lubri- cants and fragrances.
- the core can be prepared by granulating the blend, e.g. by use of granulation techniques including: crystallisation, precipitation, pan-coating, fluid bed coating, fluid bed agglomeration, rotary atomization, extrusion, prilling, spheronization, size reduction methods, drum granulation, and/or high shear granulation.
- granulation techniques including: crystallisation, precipitation, pan-coating, fluid bed coating, fluid bed agglomeration, rotary atomization, extrusion, prilling, spheronization, size reduction methods, drum granulation, and/or high shear granulation.
- the core may consist of an inert particle with the blend absorbed into it, or with the blend applied on to the surface e.g. via fluid bed coating.
- the core particle may have a diameter of 20-2000 ⁇ , particularly 50-1500 ⁇ , 100- 1500 m or 250-1200 ⁇ .
- the core of the granule comprises an enzyme, e.g. an amylase, a carbohydrase, a protease, a lipase, a cellulase, an oxidoreductase, a mannanase or a pectate lyase.
- an enzyme e.g. an amylase, a carbohydrase, a protease, a lipase, a cellulase, an oxidoreductase, a mannanase or a pectate lyase.
- the granules of the invention typically include between about 0.005 to about 500 mg/g on a dry weight basis of the enzyme component relative to the core (as active enzyme protein).
- the amount of enzyme in embodiments of the invention comprises about 0.05 to 300 mg/g, about 0.1 to 250 mg/g, about 0.5 to 200 mg/g, about 0.5 to 200 mg/g, about 1 .0 to 150 mg/g in the granule, or about 5.0 to 150 mg/g relative to the core.
- the amylase may be an a-amylase obtained from Bacillus, e.g. B. subtilis and B. Iicheniformis, in particular the amylase from a special strain of B. Iicheniformis, described in more detail in GB 1 ,296,839.
- WO 94/02597 examples include WO 94/18314, WO 1995/010603, WO 1995/026397, WO 96/23873, WO 97/43424, and WO 00/60060, WO 2001/066712, WO 2006/002643, especially the variants with substitutions in one or more of the following positions: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181 , 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391 , 408, and 444.
- the alpha-amylase is derived from Bacillus sp. strains NCIB 12289, NCIB 12512, NCIB 12513 and DSM 9375. Especially preferred are the alpha-amylases shown in SEQ ID NOS 1 and 2 of WO 95/26397.
- amylases are NATALASETM, STAI NZYMETM, STAI NZYME PLUSTM, TERMAMYLTM U LTRA, DU RAMYLTM, TERMAMYLTM, FUNGAMYLTM and BANTM (Novozymes A/S), RAPIDASETM, PURASTARTM and PURASTAR OXAMTM (from Genencor International Inc.).
- Suitable proteases include those of animal, vegetable or microbial origin. Microbial origin is preferred. Chemically modified or protein engineered mutants are included.
- the protease may be a serine protease or a metalloprotease, preferably an alkaline microbial protease or a trypsin-like protease.
- alkaline proteases are subtilisins, especially those derived from Bacillus, e.g., subtilisin Novo, subtilisin Carlsberg, subtilisin 309, subtilisin 147 and subtilisin 168 (described in WO 89/06279).
- Examples of trypsin-like proteases are trypsin (e.g., of porcine or bovine origin) and the Fusarium protease described in WO 89/06270 and WO 94/25583.
- Examples of useful proteases are the variants described in WO 92/19729, WO 98/201 15, WO 98/201 16, and WO 98/34946, especially the variants with substitutions in one or more of the following positions: 27, 36, 57, 76, 87, 97, 101 , 104, 120, 123, 167, 170, 194, 206, 218, 222, 224, 235, and 274.
- Preferred commercially available protease enzymes include AlcalaseTM, SavinaseTM, PrimaseTM, DuralaseTM, EsperaseTM, and KannaseTM (Novozymes A/S), MaxataseTM, MaxacalTM, MaxapemTM, ProperaseTM, PurafectTM, Purafect OxPTM, FN2TM, and FN 3TM (Genencor International Inc.).
- the lipase may be Thermomyces lanuginosus lipase (TLL, shown as SEQ ID NO: 2 in WO 2009/109500), Alcaligenes sp. lipase, Achromobacter sp. lipase, Burkholderia cepacia li- pase, Pseudomonas stutzeri lipase, or it may be a variant which has an amino sequence with at least 80% identity to one of these, particularly at least 85%, at least 90%, at least 95% or at least 98% identity.
- TLL Thermomyces lanuginosus lipase
- TLL homologues are described in WO 1992/005249, Lipolase Ultra), WO0060063, WO9707202, WO0032758, WO02055679, WO04099400, WO07087508 and WO 2009/109500.
- Commercial lipases include the following products of Novozymes A/S: Novo- zymTM 435, Novozym 735, LipozymeTM RM, Novozym 388, Lipolase UltraTM, LipexTM, Lipopri- meTM, LipolaseTM, LipocleanTM and LipolexTM.
- Suitable cellulases include complete cellulases or mono-component endoglucanases of bacterial or fungal origin. Chemically or genetically modified mutants are included.
- the cellulase may for example be a mono-component or a mixture of mono-component endo-1 ,4-beta- glucanase often just termed endoglucanases (EC 3.2.1.4).
- Some xyloglucanases may also have endoglucanase activity and are also considered as suitable cellulases in the present invention.
- Suitable cellulases are disclosed in US 4,435,307, which discloses fungal cellulases produced from Humicola insolens. Especially suitable cellulases are the cellulases having textile care benefits. Examples of such cellulases are cellulases described in European patent applica- tion No. 0 495 257.
- Suitable mono-component endoglucanases may be obtained from one or more of the following species Exidia glandulosa, Crinipellis scabella, Fomes fomentarius, Spongipellis sp., Rhizophlyctis rosea, Rhizomucor pusillus, Phycomyces nitens, and Chaetostylum fresenii, Dip- lodia gossypina, Microsphaeropsis sp., Ulospora bilgramii, Aureobasidium sp., Macrophomina phaseolina, Ascobolus stictoides, Saccobolus dilutellus, Peziza, Penicillium verruculosum, Peni- cillium chrysogenum, and Thermomyces verrucosus, Trichoderma reesei aka Hypocrea jecori- na, Diaporthe syngenesia, Colletotrichum lagenarium
- Cylindrocarpon sp. Nectria pinea, Volutella colletotri- choides, Sordaria fimicola, Sordaria macrospora, Thielavia thermophila, Syspastospora boni- nensis, Cladorrhinum foecundissimum, Chaetomium murorum, Chaetomium virescens, Chae- tomium brasiliensis, Chaetomium cunicolorum, Myceliophthora thermophila, Gliocladium cate- nulatum, Scytalidium thermophila, Acremonium sp Fusarium solani, Fusarium anguioides, Fusa- rium poae, Fusarium oxysporum ssp.
- lycopersici Fusarium oxysporum ssp. passiflora, Humicola nigrescens, Humicola grisea, Fusarium oxysporum, Thielavia terrestris or Humicola insolens.
- One preferred endoglucanase is disclosed in WO 96/29397 as SEQ I D NO: 9 (hereby incorporated by reference) or an enzyme with at least 70% identity thereto and variants thereof as disclosed in Example 1 of WO 98/12307.
- Another preferred endoglucanase is disclosed in WO 91/017243 (SEQ ID NO:2) or endoglucanases variants as disclosed in WO 94/007998.
- Endoglucanases with an anti-redeposition effect may be obtained from fungal endoglu- canases lacking a carbohydrate-binding module (CBM) from a number of bacterial sources.
- Some sources are Humicola insolens, Bacillus sp. deposited as DSM 12648, Bacillus sp. KSMS237 deposited as FERM P-16067, Panibacillus polymyxa, and Panibacillus pabuli.
- Specific anti-redeposition endoglucanase are disclosed in WO 91/17244 (fig.
- Xyloglucanases with an anti-redeposition effect may be obtained from a number of bacterial sources. Some sources are Bacillus licheniformis, Bacillus agaradhaerens, (WO 99/02663) Panibacillus polymyxa, and Panibacillus pabuli (WO01/62903). Suitable variants of xyloglucasnes are also described in PCT/EP2009/056875. A commercially available xylogluca- nase is Whitezyme ® (Novozymes A/S).
- cellulases include Celluclast ® produced from Trichoderma ree- sei, Celluzyme ® produced from Humicola insolens.
- Commercially available endoglucanases are Carezyme ® , Renozyme ® , Endolase ® and Celluclean ® (Novozymes A/S), and KAC-500(B)TM (Kao Corporation) and ClazinaseTM, PuradaxTM EG L and Puradax HA (Danisco A/S).
- the pectate lyase may be a wild-type enzymes derived from Bacillus, particularly B. li- cherniformis or B. agaradhaerens, or a variant derived of these, e.g. as described in US 6,124,127 (NZ 5543), WO 1999/027083 (NZ 5377), WO 1999/027084 (NZ 5378), WO 2002/006442 (NZ 10044), WO 2002/092741 (NZ 10171 ), or WO 2003/095638 (NZ 10190).
- the mannanase may be an alkaline mannanase of Family 5 or 26. It may be a wild- type from Bacillus or Humicola, particularly B. agaradhaerens, B. licheniformis, B. halodurans, B. clausii, or H. insolens. Suitable mannanases are described in WO 1999/064619 (NZ 5440). Reducing agent, peroxide decomposing catalyst and/or antioxidant
- the granule contains a reducing agent, a peroxide decomposing catalyst and/or an antioxidant (a molecule capable of slowing or preventing the oxidation of other molecules) in the core and/or in the coating.
- a reducing agent e.g. a peroxide decomposing catalyst
- an antioxidant a molecule capable of slowing or preventing the oxidation of other molecules
- examples are sulfites, thiosulfates, erythorbates, ascorbates and nitrites, e.g. as salts of alkali metals and earth alkali metals.
- Suitable materials are methionine, cysteine, propyl gallate, tert-butyl hydroquinone, tocopherols, thiodipropionic acid, butylated hy- droxytoluene (BHT), butylated hydroxyanisol (BHA) or tannic acid.
- transition metals as reducing agents and/or peroxide decomposing catalysts like e.g. V, Co, Mn and Fe, typically as salts, e.g. sulfate-, acetate-, nitrate or chloride- salts or oxides, e.g. FeS0 4 , FeCI 3 , CoSQ 4 , MnS0 4 or MnQ 2 . Water soluble salts of the transition metals are preferred.
- peroxide decomposing catalysts also an enzyme can be used, e.g. catalase.
- the amount of the antioxidant, peroxide decomposing catalyst or reducing agent may be at least 0.1 % by weight relative to the core, particularly at least 0.2 %, at least 0.5 %, at least 1 %, or at least 1 % The amount may be at most 10% by weight relative to the core, particularly at most 5%, at most 4 %, at most 3 % or at most 2 %.
- the amount of a salt is calculated in anhydrous form.
- Peroxide decomposing catalysts can be efficient in even lower concentrations, e.g. at least 0.001 %, or at least 0.01 %; the amount may be at most 5 % or at most 1 %.
- the granule contains a salt of a multivalent cation in the core, particularly a divalent or trivalent cation, e.g. a salt of Mg, Zn, Cu, Mn, Ca or Al.
- the salt may include an organic or inorganic anion such as sulfate, chloride or acetate.
- Particular salts include magnesium sulfate and zinc sulfate, e.g. magnesium sulfate heptahydrate.
- the salt may be used in an amount of at least 0.1 % by weight of the core, particularly at least 0.5% by weight, e.g. at least 1 % by weight.
- the amount may be at most 15 %, 10 % or 5 %.
- the percentage indicates the amount of the salt in anhydrous form.
- the multivalent cation may be used in an amount of at least 0.02% by weight of the core, particularly at least 0.1% by weight, e.g. at least 0.2 % by weight.
- the amount may be at most 6 %, at most 4 % or at most 2 %.
- the percentage indicates the amount of the multi- valent cation.
- the granule contains an acidic buffer component (acidic buffering agent) in the core or the coating.
- the amount may be at least 0.1 by weight of the core, particularly at least 1 % by weight.
- the amount is typipcally at most 10% by weight of the core, particularly at most 5% by weight. The percentage indicates the amount in anhydrous form.
- the acidic buffer component has a pH below 7 when measured as a 1 % by weight aqueous solution (or alternatively a 10% solution).
- the acidic buffer component may have a pH of 1 to below 7, e.g. a pH of 3 to below 7, particularly a pH of 4 to 5.
- the acidic buffer component is typically a mixture comprising a weak acid and the corresponding base; it is at least partly in its acid form
- the acidic buffer component has a pKa from 2 to 9, in particular a pK a from
- a pK a from 5 to 8 in particular a pK a from 2 to 6, in particular a pK a from 2 to 5, in particular a pK a from 2 to 4, in particular a pK a from 5 to 7.
- the pH of an aqueous solution is in general below the pK a .
- Particularly suitable acidic buffer components are salts of H 3 P0 4 e.g. NaH 2 P0 4 , KH 2 P0 4 , and Ca(H 2 P0 4 ) 2 , polyphosphates e.g. sodium hexametaphosphate, polyacrylic acid and partly neutralized polyacrylic acid and co-polymers thereof, simple organic acids (less than 10 carbon atoms e.g. 6 or less carbon atoms) such as citric acid and salts thereof such as hydrogen citrate, e.g. disodium hydrogen citrate, malonic, succinic, glutaric, adipic acid.
- H 3 P0 4 e.g. NaH 2 P0 4 , KH 2 P0 4 , and Ca(H 2 P0 4 ) 2
- polyphosphates e.g. sodium hexametaphosphate
- simple organic acids less than 10 carbon atoms e.g. 6
- the acidic buffer components are selected from the group consisting of polyacrylic acid and partly neutralized polyacrylic acid and co-polymers thereof, citric acid and Na 3 -citrate.
- the granule comprises a core surrounded by at least one coating.
- the coating may comprise at least 60% by weight w/w of a salt, e.g. at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95% or at least 99% by weight w/w.
- the coating may be applied in an amount of at least 5 % by weight of the core, e.g. at least 10%, 10% or 15%.
- the amount may be at most 70 %, 50 %, 40 % or 30%.
- the salt coating is preferably at least 1 ⁇ thick, particularly at least 2 ⁇ , at least 4 ⁇ or at least 8 ⁇ .
- the thickness of the salt coating is below 100 ⁇ .
- the thickness of the salt coating is below 60 ⁇ .
- the total thickness of the salt coating is below 40 ⁇ .
- the coating should encapsulate the core unit by forming a substantially continuous layer.
- a substantially continuous layer is to be understood as a coating having few or no holes, so that the core unit it is encapsulating has few or none uncoated areas.
- the layer or coating should in particular be homogenous in thickness.
- the salt may be added from a salt solution where the salt is compSetely dissolved or from a salt suspension wherein the fine particles is less than 50 ⁇ , such as less than 10 ⁇ or less than 5 ⁇ .
- the salt coating is especially effective if it is applied in a fluid bed under relatively high humidity conditions.
- the reducing agent/antioxidant/peroxide decomposing catalyst may be part of the salt coating, either as a homogeneous part of the entire salt coating, or as part of this coating, e.g. only as an inner layer of salt and /antioxidant/peroxide decomposing catalyst.
- Using e.g. FeS0 4 as a reducing agent/peroxide decomposing catalyst may induce a color change as the metal is oxidized, which can be hidden by having the component as an inner layer.
- the salt coating can further contain other materials as known in the art, e.g. fillers, an- tisticking agents, pigments, dyes, plasticizers andf/or binders, such as titanium dioxide, kaolin, calcium carbonate or talc. Salts
- the salt coating may comprise a single salt or a mixture of two or more salts.
- the salt may be water soluble, in particular having a solubility at least 0.1 grams in 100 g of water at 20°C, preferably at least 0.5 g per 100 g water, e.g. at least 1 g per 100 g water, e.g. at least 5 g per 100 g water.
- the salt may be an inorganic salt, e.g. salts of sulfate, sulfite, phosphate, phosphonate, nitrate, chloride or carbonate or salts of simple organic acids (less than 10 carbon atoms e.g. 6 or less carbon atoms) such as citrate, malonate or acetate.
- simple organic acids less than 10 carbon atoms e.g. 6 or less carbon atoms
- Examples of cations in these salt are alkali or earth alkali metal ions, the ammonium ion or metal ions of the first transition series, such as sodium, potassium, magnesium, calcium, zinc or aluminium.
- anions include chloride, bromide, iodide, sulfate, sulfite, bisulfite, thiosulfate, phosphate, monobasic phosphate, dibasic phosphate, hypophosphite, dihydrogen pyrophosphate, tetraborate, borate, carbonate, bicarbonate, metasilicate, citrate, malate, maleate, malonate, succinate, lactate, formate, acetate, butyrate, propionate, benzoate, tartrate, ascorbate or gluconate.
- al- kali- or earth alkali metal salts of sulfate, sulfite, phosphate, phosphonate, nitrate, chloride or carbonate or salts of simple organic acids such as citrate, malonate or acetate may be used.
- Specific examples include NaH 2 P0 4 , Na 2 HP0 4 , Na 3 P0 4 , (NH 4 )H 2 P0 4 , K 2 HP0 4 , KH 2 P0 4 , Na 2 S0 4 , K 2 S0 4 , KHS0 4 , ZnS0 4 , MgS0 4 , CuS0 4 , Mg(N0 3 ) 2 , (NH 4 ) 2 S0 4 , sodium borate, magnesium acetate and sodium citrate.
- the salt may be in anhydrous form, or it may be a hydrated salt, i.e. a crystalline salt hydrate with bound water(s) of crystallization, such as described in WO 99/32595.
- Specific examples include anhydrous sodium sulfate (Na 2 S0 4 ), anhydrous magnesium sulfate (MgS0 4 ), magnesium sulfate heptahydrate (MgS0 4 (7H 2 0)), zinc sulfate heptahydrate (ZnS0 4 (7H 2 0)), sodium phosphate dibasic heptahydrate (Na 2 HP0 4 (7H 2 0)), magnesium nitrate hexahydrate (Mg(N0 3 ) 2 (6H 2 0)), sodium borate decahydrate, sodium citrate dihydrate and magnesium acetate tetrahydrate.
- the salt in the coating may have a constant humidity at 20°C above 60%, particularly above 70%, above 80% or above 85% by weight, or it may be another hydrate form of such a salt (e.g. anhydrate).
- the salt coating may be according to WO 00/01793, which is hereby in- corporated by reference.
- the salt is selected from the group consisting of NaCI, Na 2 C0 3 , NaN0 3 , Na 2 HP0 4 , Na 3 P0 4 , NH 4 CI, (NH 4 ) 2 HP0 4 , NH 4 H 2 P0 4 , (NH 4 ) 2 S0 4 , KCI, K 2 HP0 4 , KH 2 P0 4 , KN0 3 , Na 2 S0 4 , K 2 S0 4 , KHS0 4 , MgS0 4 , ZnS0 4 , NaCI and sodium citrate or mixtures thereof.
- the salt is selected from the group consisting of NaCI, Na 2 C0 3 , NaN0 3 , Na 2 HP0 4 , Na 3 P0 4 , NH 4 CI, (NH 4 ) 2 HP0 4 , NH 4 H 2 P0 4 , (NH 4 ) 2 S0 4 , KCI, K 2 HP0 4 , KH 2 P0 4 , KNO 3 , Na 2 S0 4 , K 2 S0 4 , KHS0 4 , NaCI and sodium citrate or mixtures thereof.
- the salt comprised in the coating of the granule is selected from the group consisting of NaCI, Na 2 C0 3 , NaN0 3 , Na 2 HP0 4 , Na 3 P0 4 , NH 4 CI, (NH 4 ) 2 HP0 4 , NH 4 H 2 P0 4 , (NH 4 ) 2 S0 4 , KCI, K 2 HP0 4 , KH 2 P0 4 , KN0 3 , Na 2 S0 4 , K 2 S0 4 , KHS0 4 , MgS0 4 , ZnS0 4 , NaCI and sodium citrate or mixtures thereof.
- the salt it applied as a solution of the salt e.g. using a fluid bed.
- the granule may include an additional coating on the outside of the salt coating, e.g. in an amount of at least 0.5% by weight of the core, particularly at least 1 %, e.g. at most 20 % or 10 %.
- the additional coating may comprise polyethylene glycol (PEG), hydroxy- propyl methyl cellulose (HPMC or MHPC), polyvinyl alcohol (PVA) or other film forming agents and can further contain fillers, antisticking agents, pigment, dye, plasticizers etc.
- the granules are particularly suited for incorporation in a granular detergent composition comprising a surfactant.
- Enzyme granules according to the invention result in improved sto- rage stability of the enzyme when the granules are incorporated in a detergent, even a detergent comprising aggressive components such as a bleaching system.
- the detergent composition may for example be formulated as a laundry detergent composition for hand or machine washings including a cleaning additive composition suitable for pre-treatment of stained fabrics or a fabric softener composition, or a detergent composition for use in general household hard surface cleaning operations, or a composition for hand or machine dishwashing operations.
- the detergent composition of the invention may be in any convenient dry form, e.g., a bar, a tablet, a powder, a granulate or a paste. It may also be a liquid detergent, either an aqueous or non-aqueous liquid detergent.
- the detergent composition comprises one or more surfactants, which may be non-ionic including semi-polar and/or anionic and/or cationic and/or zwitterionic.
- the surfactants are typically present at a level of from 0.1 % to 60% by weight.
- the detergent When included therein the detergent will usually contain from about 1 % to about 40% of an anionic surfactant such as linear alkylbenzenesulfonate, alpha-olefinsulfonate, alkyl sulfate (fatty alcohol sulfate), alcohol ethoxysulfate, secondary alkanesulfonate, alpha-sulfo fatty acid methyl ester, alkyl- or alkenylsuccinic acid or soap.
- an anionic surfactant such as linear alkylbenzenesulfonate, alpha-olefinsulfonate, alkyl sulfate (fatty alcohol sulfate), alcohol ethoxysulfate, secondary alkanesulfonate, alpha-sulfo fatty acid methyl ester, alkyl- or alkenylsuccinic acid or soap.
- the detergent When included therein the detergent will usually contain from about 0.2% to about 40% of a non-ionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanola- mide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine ("gluca- mides").
- a non-ionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanola- mide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine ("gluca- mides").
- the detergent composition may comprise one or more surfactants, which may be anionic and/or cationic and/or non-ionic and/or semi-polar and/or zwitterionic, or a mixture thereof.
- the detergent composition includes a mixture of one or more nonionic surfactants and one or more anionic surfactants.
- the surfactant(s) is typically present at a level of from about 0.1 % to 60% by weight, such as about 1 % to about 40%, or about 3% to about 20%, or about 3% to about 10%.
- the detergent When included therein the detergent will usually contain from about 1 % to about 40% by weight, such as from about 5% to about 30%, including from about 5% to about 15%, or from about 20% to about 25% of an anionic surfactant.
- anionic surfactants include sulfates and sulfonates, in particular, linear alkylbenzenesulfonat.es (LAS), branched alkylbenze- nesulfonates (BABS), phenylalkanesulfonat.es, alpha-olefinsulfonates (AOS), olefin sulfonates, al- kene sulfonates, alkane-2,3-diylbis(sulfates), hydroxyalkanesulfonat.es and disulfonates, alkyl sulfates (AS) such as sodium dodecyl sulfate (SDS), fatty alcohol sulfates (FAS), primary alcohol sul
- Non-limiting examples of cationic surfactants include alklydimethylehanolamine quat (ADMEAQ), cetyltrimethylammonium bromide (CTAB), dimethyldistearylammonium chloride (DSDMAC), and alkylbenzyldimethylammonium, and combinations thereof.
- the detergent will usually contain from about 0.2% to about 40% by weight of a non-ionic surfactant, for example from about 0.5% to about 30%, in particular from about 1 % to about 20%, from about 3% to about 10%, such as from about 3% to about 5%, or from about 8% to about 12%.
- Non-limiting examples of non-ionic surfactants include alcohol ethoxylates (AE or AEO), alcohol propoxylates, propoxylated fatty alcohols (PFA), alkoxylated fatty acid alkyl esters, such as ethoxylated and/or propoxylated fatty acid alkyl esters, alkylphenol ethoxylates (APE), nonylphenol ethoxylates (NPE), alkylpolyglycosides (APG), alkoxylated amines, fatty acid monoethanolamides (FAM), fatty acid diethanolamides (FADA), ethoxylated fatty acid monoetha- nolamides (EFAM), propoxylated fatty acid monoethanolamide (PFAM), polyhydroxy alkyl fatty acid amides, or N-acyl N-alkyl derivatives of glucosamine (glucamides, GA, or fatty acid glucamide, FAGA), as well as products available under the trade names SPAN and TW
- Non-limiting examples of semipolar surfactants include amine oxides (AO) such as alkyl- dimethylamineoxide, /V-(coco alkyl)-/V,/V-dimethylamine oxide and /V-(tallow-alkyl)-/V,/V-bis(2- hydroxyethyl)amine oxide, fatty acid alkanolamides and ethoxylated fatty acid alkanolamides, and combinations thereof.
- AO amine oxides
- Non-limiting examples of zwitterionic surfactants include betaine, alkyldimethylbetaine, and sulfobetaine, and combinations thereof.
- the detergent may contain 0-65 % of a detergent builder or complexing agent such as zeolite, diphosphate, triphosphate, phosphonate, carbonate, citrate, nitrilotriacetic acid, ethyle- nediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl- or alkenylsuccinic acid, soluble silicates or layered silicates (e.g. SKS-6 from Hoechst).
- a detergent builder or complexing agent such as zeolite, diphosphate, triphosphate, phosphonate, carbonate, citrate, nitrilotriacetic acid, ethyle- nediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl- or alkenylsuccinic acid, soluble silicates or layered silicates (e.g. SKS-6 from Hoechst).
- the level of builder is typically 40-65%, particularly 50-65%.
- the builder and/or co-builder may particularly be a chelating agent that forms water-soluble complexes with Ca and Mg.
- Non-limiting examples of builders include zeolites, diphosphates (pyrophosphates), triphosphates such as sodium triphosphate (STP or STPP), carbonates such as sodium carbonate, soluble silicates such as sodium metasilicate, layered silicates (e.g., SKS- 6 from Hoechst), ethanolamines such as 2-aminoethan-1 -ol (MEA), iminodiethanol (DEA) and 2,2',2"-nitrilotriethanol (TEA), and carboxymethylinulin (CMI), and combinations thereof.
- zeolites diphosphates (pyrophosphates), triphosphates such as sodium triphosphate (STP or STPP), carbonates such as sodium carbonate, soluble silicates such as sodium metasilicate,
- the detergent composition may include include a co-builder alone, or in combination with a builder, for example a zeolite builder.
- co-builders include homo- polymers of polyacrylates or copolymers thereof, such as poly(acrylic acid) (PAA) or copo- ly(acrylic acid/maleic acid) (PAA PMA).
- PAA poly(acrylic acid)
- PAA PMA copo- ly(acrylic acid/maleic acid)
- Further non-limiting examples include citrate, chelators such as aminocarboxylates, aminopolycarboxylates and phosphonates, and alkyl- or alkenyl- succinic acid.
- NTA 2,2',2"-nitrilotriacetic acid
- EDTA etheylene- diaminetetraacetic acid
- DTPA diethylenetriaminepentaacetic acid
- IDS iminodisuccinic acid
- EDDS ethylenediamine-N,N'-disuccinic acid
- MGDA methylglycinediacetic acid
- GLDA glutamic acid-N,N-diacetic acid
- HEDP ethylenediaminetetrakis(methylene)tetrakis(phosphonic acid)
- DTPMPA diethylenetriamine- pentakis(methylene)pentakis(phosphonic acid)
- EDG 2,2',2"-nitrilotriacetic acid
- EDTA etheylene- diaminetetraacetic acid
- DTPA diethylenetriaminepentaacetic acid
- IDS iminodisuccinic acid
- EDDS ethylenediamine-
- the detergent may comprise one or more polymers.
- Examples are carboxymethylcellu- lose, poly(vinylpyrrolidone), poly (ethylene glycol), polyvinyl alcohol), poly(vinylpyridine-N- oxide), poly(vinylimidazole), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
- the detergent may contain a bleaching system, which may comprise a H2O2 source such as perborate or percarbonate, which may be combined with a peracid-forming bleach activator such as tetraacetylethylenediamine or nonanoyloxybenzenesulfonate.
- a bleaching system may comprise peroxyacids of e.g. the amide, imide, or sulfone type.
- Suitable bleaching system components include bleaching catalysts, photobleaches, bleach activators, sources of hydrogen peroxide such as sodium percarbonate and sodium per- borates, preformed peracids and mixtures thereof.
- Suitable preformed peracids include, but are not limited to, peroxycarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, for example, Oxone (R), and mixtures thereof.
- Non- limiting examples of bleaching systems include peroxide-based bleaching systems, which may comprise, for example, an inorganic salt, including alkali metal salts such as sodium salts of per- borate (usually mono- or tetra-hydrate), percarbonate, persulfate, perphosphate, persilicate salts, in combination with a peracid-forming bleach activator.
- Suitable photobleaches may for example be sulfonated zinc phthalocyanine.
- Suitable bleach activators include 4- (dodecanoyloxy)benzenesulfonate (LOBS), 4-(decanoyloxy)benzenesulfonate, 4- (decanoyloxy)benzoate (DOBS), 4-(3,5,5-trimethylhexanoyloxy)benzenesulfonate (ISONOBS), tetraacetylethylenediamine (TAED) and 4-(nonanoyloxy)benzenesulfonate (NOBS), and/or those disclosed in W098/17767.
- the bleaching system may comprise peroxyacids of, for example, the amide, imide, or sulfone type.
- the bleaching system may also comprise pera- cids such as 6-(phthaloylamino)percapronic acid (PAP).
- PAP 6-(phthaloylamino)percapronic acid
- the bleaching system may also include a bleach catalyst.
- the bleach component may be an organic catalyst se- lected from the group consisting of organic catalysts having the following formulae:
- each R 1 is independently a branched alkyl group containing from 9 to 24 carbons or linear alkyl group containing from 1 1 to 24 carbons, preferably each R 1 is independently a branched alkyl group containing from 9 to 18 carbons or linear alkyl group containing from 1 1 to 18 carbons, more preferably each R 1 is independently selected from the group consisting of 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n- dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, iso-nonyl, iso-decyl, iso- tridecyl and iso- pentadecyl.
- Other exemplary bleaching systems are described, e.g., in WO2007/087258, WO2007/087244, WO2007
- a hydrotrope is a compound that solubilises hydrophobic compounds in aqueous solu- tions (or oppositely, polar substances in a non-polar environment).
- hydrotropes have both hydrophilic and a hydrophobic character (so-called amphiphilic properties as known from surfactants); however the molecular structure of hydrotropes generally do not favor spontaneous self-aggregation, see e.g. review by Hodgdon and Kaler (2007), Current Opinion in Colloid & I nterface Science 12: 121 -128. Hydrotropes do not display a critical concentration above which self-aggregation occurs, as found for surfactants and lipids forming miceller, lamellar or other well defined meso-phases.
- hydrotropes show a continuous-type aggregation process where the size of aggregates grow as concentration increases.
- many hydrotropes alter the phase behavior, stability, and colloidal properties of systems containing substances of polar and non-polar character, including mixtures of water, oil, surfactants, and polymers.
- Hydrotropes are classically used across industries from pharma, personal care, food, to technical applications.
- Use of hydrotropes in detergent compositions allow for example more concentrated formulations of surfactants (as in the process of compacting liquid detergents by removing water) without inducing undesired phenomena such as phase separation or high viscosity.
- the detergent may contain 0-5% by weight, such as about 0.5 to about 5%, or about 3% to about 5%, of a hydrotrope.
- hydrotropes include sodium benzene sulfonate, sodium p-toluene sulfonates (STS), sodium xylene sulfonates (SXS), sodium cumene sulfonates (SCS), sodium cymene sulfonate, amine oxides, alcohols and polyglycolethers, sodium hydroxynaphthoate, sodium hydroxynaphthalene sulfonate, sodium ethylhexyl sulfate, and combinations thereof. Fabric hueing agents
- the detergent compositions of the present invention may also include fabric hueing agents such as dyes or pigments which when formulated in detergent compositions can deposit onto a fabric when said fabric is contacted with a wash liquor comprising said detergent compositions thus altering the tint of said fabric through absorption/reflection of visible light.
- fabric hueing agents alter the tint of a surface as they absorb at least a portion of the visible light spectrum.
- Suitable fabric hueing agents include dyes and dye-clay conjugates, and may also include pigments.
- Suitable dyes include small molecule dyes and polymeric dyes.
- Suitable small molecule dyes include small molecule dyes selected from the group consisting of dyes falling into the Colour Index (C.I.) classifications of Direct Blue, Direct Red, Direct Violet, Acid Blue, Acid Red, Acid Violet, Basic Blue, Basic Violet and Basic Red , or mixtures thereof, for example as described in WO2005/03274, WO2005/03275, WO2005/03276 and EP1876226 (hereby incorporated by reference).
- the detergent composition preferably comprises from about 0.00003 wt% to about 0.2 wt%, from about 0.00008 wt% to about 0.05 wt%, or even from about 0.0001 wt% to about 0.04 wt% fabric hueing agent.
- the composition may comprise from 0.0001 wt% to 0.2 wt% fabric hueing agent, this may be especially preferred when the composition is in the form of a unit dose pouch .
- a ble h uei ng agents a re a lso d isclosed i n , e. g . , WO 2007/087257, WO2007/087243.
- the enzyme granules may be included in a granular detergent formulated as described in WO09/092699, EP1705241 , EP1382668, WO07/001262, US6472364, WO04/074419 or WO09/102854.
- a typical formulation is a high-shear T-granulate as produced e.g. in example 1 of WO 2004/003188 (Int'l Appl. No. PCT/DK03/000456) (containing enzyme, Na-sulfate, cellulose fibers, calcium carbonate and a binder, e.g. sucrose or dextrin) with the following formulation in the core (% by weight of uncoated dry granulate):
- Citric acid monohydrate to a pH in the enzyme concentrate feed of 4.5-5)
- These stabilizers are preferably added to the aqueous enzyme concentrate before granulation.
- Na-sulfate coating is applied under relatively humid condition (around 50% by weight RH in the outgoing air) in a fluid bed (e.g. as produced in example 4 of WO03/000456).
- a cosmetic and dust reducing outer thin film is further applied in fluid bed (e.g. PEG4000, kaolin and Ti0 2 ).
- the residual activity is based on wash performance analysis, i.e. 50% residual activity indicates that the washing performance after storage corresponds to that of unstored detergent with 50% dosage of the enzyme .
- the residual activity is typically less than 10% by weight if one of the stabilizing techniques are excluded, and typically > 75% by weight if all four techniques are present.
- Wash performance is measured using a a mini-wash robot (60 ml wash solution) with a bleach containing detergent using a water hardness of 15°dH, wash at 40°C in 30 minutes, de- tergent dosage 5 g/L and measure reflectance (460 nm on a Zeiss spectrophotometer) on rice starch based swatches (CS-28 from CFT of Holland)
- amylase granulate is made with the following composition. The amounts are given in relation to the raw (uncoated) granulate. The granules are made by high shear granulation and coated by fluid bed coating
- a number of enzyme granulates were prepared by mixing enzyme and stabilizers as shown in the table below and granulating in a mixer. A salt coating and film coating were ap- plied as indicated. Each granulate was then added to a granular bleach detergent and stored at 37 ° C, 70% relative humidity. The enzymes tested were two Bacillus amylase variants (denoted Amylase X and Y, respectively). Amounts are given as % by weight in relation to the weight of the core. The film coating was applied in an amount of 3 % by weight of the core. The film coating consisted of Sepifilm LP030 (A mixture of Hypromellose (HPMC) as film forming polymer, Micro-Crystalline Cellulose (MCC) and Stearic acid).
- Sepifilm LP030 A mixture of Hypromellose (HPMC) as film forming polymer, Micro-Crystalline Cellulose (MCC) and Stearic acid).
- amylase granulates were produced as a high-shear T-granulate as in Example 2 of WO 2004/003188 (based on aqueous amylase concentrate, cellulose fibers and Na-sulfate as filler). After granulation and drying Na-sulfate coatings were applied (from a Na-sulfate solution) in a fluid bed.
- the storage stability of the granulates was evaluated by determining the wash performance after 3 days and 7 days storage. The results are shown below (wash performance based storage stability data given in % residual activity as described above).
- a Cellulase granulate was produced as a high-shear T-granulate as in example 2 of WO 2004/003188 (based on Cellulose fibers and Na-sulfate as filler) and including in the core the following stabilizers (% by weight of uncoated dry granulate):
- Citric acid monohydrate to a pH in the enzyme concentrate feed of 4.5-5
- the stabilizers were added to the aqueous enzyme concentrate before granulation.
- Na-sulfate:Ti0 2 25:2 w/w coating was applied (from a 25:2:73 Na-sulfate: Ti0 2 :water solution) in a fluid bed.
- a cosmetic and dust reducing outer thin film was further applied in fluid bed (2.5% PEG4000:TiO 2 1 :1 w/w).
- a Cellulase granulate was produced as a high-shear T-granulate as in Example 2 of WO 2004/003188 (based on Cellulose fibers and Na-sulfate as filler) without addition of stabilizers
- Na-sulfate:Ti0 2 25:2 w/w coating was applied (from a 25:2:73 Na-sulfate:Ti0 2 :water solution) in a fluid bed.
- a cosmetic and dust reducing outer thin film was further applied in fluid bed (2.5% PEG4000:TiO 2 1 :1 w/w).
- alkaline protease granulate was produced as a high-shear T-granulate as in exam- pie 2 of WO 2004/003188 (based on spray-dried protease, Cellulose fibers and Na-sulfate as filler) with the following stabilizers in the core (% by weight of uncoated dry granulate):
- the stabilizers were added to the granulation liquid (water) before granulation.
- alkaline protease granulate was produced as a high-shear T-granulate as in example 2 of WO 2004/003188 (based on spray-dried protease, Cellulose fibers and Na-sulfate as filler) with the following stabilizers in the core (% by weight of uncoated dry granulate):
- the stabilizer was added to the granulation liquid (water) before granulation.
- the uncoated granulate was coated in a mixer with 6% melted PEG4000 and 14% Ti0 2 :Calcium carbonate 1 :1
- the stability in a bleach containing detergent of the 2 granulates from example 6 and 7 were tested over 2 weeks at 37°C and 70% relative humidity (residual activity measured by a standard protease assay):
- the stabilizer mixture with salt coating significantly increases storage stability of the protease.
Abstract
Description
Claims
Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201180025872.8A CN102906251B (en) | 2010-04-26 | 2011-04-15 | Enzyme granulate agent |
EP17187533.9A EP3279319B1 (en) | 2010-04-26 | 2011-04-15 | Enzyme granules |
MX2012012096A MX2012012096A (en) | 2010-04-26 | 2011-04-15 | Enzyme granules. |
RU2012150279/10A RU2573907C2 (en) | 2010-04-26 | 2011-04-15 | Granule for use in powder detergents and composition of granule detergent |
KR1020127030043A KR101904484B1 (en) | 2010-04-26 | 2011-04-15 | Enzyme granules |
MX2015013675A MX349735B (en) | 2010-04-26 | 2011-04-15 | Enzyme granules. |
AU2011246662A AU2011246662B2 (en) | 2010-04-26 | 2011-04-15 | Enzyme granules |
BR112012024674-7A BR112012024674B1 (en) | 2010-04-26 | 2011-04-15 | Granule, and, Granular Detergent Composition |
JP2013506580A JP5944887B2 (en) | 2010-04-26 | 2011-04-15 | Enzyme granules |
CA2797032A CA2797032A1 (en) | 2010-04-26 | 2011-04-15 | Enzyme granules |
EP11715914.5A EP2563910B1 (en) | 2010-04-26 | 2011-04-15 | Enzyme granules |
US13/643,008 US9107433B2 (en) | 2010-04-26 | 2011-04-15 | Enzyme granules |
ZA2012/07687A ZA201207687B (en) | 2010-04-26 | 2012-10-12 | Enzyme granules |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10161045 | 2010-04-26 | ||
EP10161045.9 | 2010-04-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011134809A1 true WO2011134809A1 (en) | 2011-11-03 |
Family
ID=42224965
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2011/056053 WO2011134809A1 (en) | 2010-04-26 | 2011-04-15 | Enzyme granules |
Country Status (14)
Country | Link |
---|---|
US (1) | US9107433B2 (en) |
EP (3) | EP2563910B1 (en) |
JP (1) | JP5944887B2 (en) |
KR (1) | KR101904484B1 (en) |
CN (2) | CN102906251B (en) |
AU (1) | AU2011246662B2 (en) |
BR (1) | BR112012024674B1 (en) |
CA (1) | CA2797032A1 (en) |
ES (1) | ES2646166T3 (en) |
MX (2) | MX2012012096A (en) |
PL (1) | PL2840134T3 (en) |
RU (1) | RU2573907C2 (en) |
WO (1) | WO2011134809A1 (en) |
ZA (1) | ZA201207687B (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014047313A (en) * | 2012-09-03 | 2014-03-17 | Pureson Corp | Liquid detergent and method for manufacturing the same |
WO2014115804A1 (en) * | 2013-01-25 | 2014-07-31 | ライオン株式会社 | Enzyme preparation for detergent, liquid detergent, and method for manufacturing same |
WO2016005392A1 (en) * | 2014-07-08 | 2016-01-14 | Novozymes A/S | Co-granulate of enzyme and bleach catalyst |
WO2016177439A1 (en) * | 2015-05-07 | 2016-11-10 | Novozymes A/S | Manganese bleach catalyst / enzyme granules for use in dishwash detergents |
WO2017204788A1 (en) * | 2016-05-24 | 2017-11-30 | Shafer Kim | Composition of probiotics and digestive enzymes and method of preparing and using the same |
EP3301152A1 (en) * | 2016-10-03 | 2018-04-04 | The Procter & Gamble Company | Spray-dried base detergent particle giving rise to a low ph in the wash |
EP2874506B1 (en) * | 2012-07-18 | 2019-04-10 | Danisco US Inc. | Method of making enzyme granules |
US10543464B2 (en) | 2015-02-10 | 2020-01-28 | Novozymes A/S | Method for mixing of particles |
WO2021156342A1 (en) | 2020-02-04 | 2021-08-12 | Novozymes A/S | Solid stabilized laccase compositions |
WO2022171872A1 (en) | 2021-02-12 | 2022-08-18 | Novozymes A/S | Stabilized biological detergents |
EP4206309A1 (en) | 2021-12-30 | 2023-07-05 | Novozymes A/S | Protein particles with improved whiteness |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9677031B2 (en) * | 2014-06-20 | 2017-06-13 | Ecolab Usa Inc. | Catalyzed non-staining high alkaline CIP cleaner |
KR101700282B1 (en) * | 2014-12-24 | 2017-01-26 | (주)엔씨티바이오 | Catalase formulation for cleaning and manufacturing method thereof |
CN104673560B (en) * | 2015-03-25 | 2017-12-29 | 山西勇宁记科技有限公司 | Particle based on biological enzymatic compositions and preparation method and application |
US20170260482A1 (en) * | 2016-03-08 | 2017-09-14 | The Procter & Gamble Company | Particles including enzyme |
US10538720B2 (en) | 2016-03-08 | 2020-01-21 | The Procter & Gamble Company | Particles including enzyme |
US20190062675A1 (en) * | 2016-03-11 | 2019-02-28 | Novozymes A/S | Manganese Bleach Catalyst Granules |
CN106434017A (en) * | 2016-09-05 | 2017-02-22 | 广西大学 | Bioactive detergent |
AU2021357757A1 (en) * | 2020-10-07 | 2023-05-25 | Novozymes A/S | New granules for animal feed |
Citations (181)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1296839A (en) | 1969-05-29 | 1972-11-22 | ||
US4435307A (en) | 1980-04-30 | 1984-03-06 | Novo Industri A/S | Detergent cellulase |
WO1989006270A1 (en) | 1988-01-07 | 1989-07-13 | Novo-Nordisk A/S | Enzymatic detergent |
WO1989006279A1 (en) | 1988-01-07 | 1989-07-13 | Novo-Nordisk A/S | Mutated subtilisin genes |
WO1991017243A1 (en) | 1990-05-09 | 1991-11-14 | Novo Nordisk A/S | A cellulase preparation comprising an endoglucanase enzyme |
WO1991017244A1 (en) | 1990-05-09 | 1991-11-14 | Novo Nordisk A/S | An enzyme capable of degrading cellulose or hemicellulose |
WO1992005249A1 (en) | 1990-09-13 | 1992-04-02 | Novo Nordisk A/S | Lipase variants |
EP0495257A1 (en) | 1991-01-16 | 1992-07-22 | The Procter & Gamble Company | Compact detergent compositions with high activity cellulase |
WO1992019729A1 (en) | 1991-05-01 | 1992-11-12 | Novo Nordisk A/S | Stabilized enzymes and detergent compositions |
WO1994002597A1 (en) | 1992-07-23 | 1994-02-03 | Novo Nordisk A/S | MUTANT α-AMYLASE, DETERGENT, DISH WASHING AGENT, AND LIQUEFACTION AGENT |
WO1994007998A1 (en) | 1992-10-06 | 1994-04-14 | Novo Nordisk A/S | Cellulase variants |
WO1994018314A1 (en) | 1993-02-11 | 1994-08-18 | Genencor International, Inc. | Oxidatively stable alpha-amylase |
WO1994025583A1 (en) | 1993-05-05 | 1994-11-10 | Novo Nordisk A/S | A recombinant trypsin-like protease |
WO1995010603A1 (en) | 1993-10-08 | 1995-04-20 | Novo Nordisk A/S | Amylase variants |
WO1995026397A1 (en) | 1994-03-29 | 1995-10-05 | Novo Nordisk A/S | Alkaline bacillus amylase |
WO1996023873A1 (en) | 1995-02-03 | 1996-08-08 | Novo Nordisk A/S | Amylase variants |
WO1996029397A1 (en) | 1995-03-17 | 1996-09-26 | Novo Nordisk A/S | Novel endoglucanases |
WO1997007202A1 (en) | 1995-08-11 | 1997-02-27 | Novo Nordisk A/S | Novel lipolytic enzymes |
WO1997043424A1 (en) | 1996-05-14 | 1997-11-20 | Genencor International, Inc. | MODIFIED α-AMYLASES HAVING ALTERED CALCIUM BINDING PROPERTIES |
WO1998012307A1 (en) | 1996-09-17 | 1998-03-26 | Novo Nordisk A/S | Cellulase variants |
WO1998017767A1 (en) | 1996-10-18 | 1998-04-30 | The Procter & Gamble Company | Detergent compositions |
WO1998020115A1 (en) | 1996-11-04 | 1998-05-14 | Novo Nordisk A/S | Subtilase variants and compositions |
WO1998020116A1 (en) | 1996-11-04 | 1998-05-14 | Novo Nordisk A/S | Subtilase variants and compositions |
WO1998034946A1 (en) | 1997-02-12 | 1998-08-13 | Massachusetts Institute Of Technology | Daxx, a novel fas-binding protein that activates jnk and apoptosis |
WO1999002663A1 (en) | 1997-07-07 | 1999-01-21 | Novo Nordisk A/S | Alkaline xyloglucanase |
WO1999027083A1 (en) | 1997-11-24 | 1999-06-03 | Novo Nordisk A/S | PECTIN DEGRADING ENZYMES FROM $i(BACILLUS LICHENIFORMIS) |
WO1999027084A1 (en) | 1997-11-24 | 1999-06-03 | Novo Nordisk A/S | Novel pectate lyases |
WO1999032595A1 (en) | 1997-12-20 | 1999-07-01 | Genencor International, Inc. | Granule with hydrated barrier material |
WO1999037746A1 (en) | 1998-01-26 | 1999-07-29 | The Procter & Gamble Company | Multi-layer detergent tablet |
US5977053A (en) | 1995-07-31 | 1999-11-02 | Bayer Ag | Detergents and cleaners containing iminodisuccinates |
WO1999064619A2 (en) | 1998-06-10 | 1999-12-16 | Novozymes A/S | Novel mannanases |
WO2000001793A1 (en) | 1998-06-30 | 2000-01-13 | Novozymes A/S | A new improved enzyme containing granule |
WO2000032758A1 (en) | 1998-11-27 | 2000-06-08 | Novozymes A/S | Lipolytic enzyme variants |
JP2000210081A (en) | 1999-01-21 | 2000-08-02 | Kao Corp | Heat-resistant alkali cellulase gene |
US6124127A (en) | 1997-11-24 | 2000-09-26 | Novo Nordisk A/S | Pectate lyase |
WO2000060060A2 (en) | 1999-03-31 | 2000-10-12 | Novozymes A/S | Polypeptides having alkaline alpha-amylase activity and nucleic acids encoding same |
WO2000060063A1 (en) | 1999-03-31 | 2000-10-12 | Novozymes A/S | Lipase variant |
WO2001062903A1 (en) | 2000-02-24 | 2001-08-30 | Novozymes A/S | Family 44 xyloglucanases |
WO2001066712A2 (en) | 2000-03-08 | 2001-09-13 | Novozymes A/S | Variants with altered properties |
WO2002006442A2 (en) | 2000-07-19 | 2002-01-24 | Novozymes A/S | Cell-wall degrading enzyme variants |
WO2002055679A2 (en) | 2001-01-10 | 2002-07-18 | Novozymes A/S | Thermostable lipolytic enzyme variant |
US6472364B1 (en) | 1998-10-13 | 2002-10-29 | The Procter & Gamble Company | Detergent compositions or components |
WO2002092741A2 (en) | 2001-05-14 | 2002-11-21 | Novozymes A/S | 0etergent compositions comprising bacillus subtilis pectate lyases |
WO2002099091A2 (en) | 2001-06-06 | 2002-12-12 | Novozymes A/S | Endo-beta-1,4-glucanase from bacillus |
WO2003000456A2 (en) | 2001-06-22 | 2003-01-03 | Konrad Seppelt | Method for carrying out local laser-induced etching of solid materials |
WO2003055967A1 (en) * | 2001-12-21 | 2003-07-10 | Novozymes A/S | Salt coatings |
WO2003095638A1 (en) | 2002-05-14 | 2003-11-20 | Novozymes A/S | Pectate lyase variants |
WO2004003188A2 (en) | 2002-07-01 | 2004-01-08 | Novozymes A/S | Stabilization of granules |
EP1382668A1 (en) | 2002-06-11 | 2004-01-21 | Unilever N.V. | Detergent tablets |
US20040033927A1 (en) | 2002-07-01 | 2004-02-19 | Novozymes A/S | Stabilization of granules |
WO2004053039A2 (en) | 2002-12-11 | 2004-06-24 | Novozymes A/S | Detergent composition comprising endo-glucanase |
WO2004067739A2 (en) | 2003-01-27 | 2004-08-12 | Novozymes A/S | Stabilization of granules |
WO2004074419A2 (en) | 2003-02-18 | 2004-09-02 | Novozymes A/S | Detergent compositions |
WO2004099400A2 (en) | 2003-05-09 | 2004-11-18 | Novozymes A/S | Variant lipolytic ensymes |
WO2005003275A1 (en) | 2003-06-18 | 2005-01-13 | Unilever Plc | Laundry treatment compositions |
WO2005003276A1 (en) | 2003-06-18 | 2005-01-13 | Unilever Plc | Laundry treatment compositions |
WO2005003274A1 (en) | 2003-06-18 | 2005-01-13 | Unilever Plc | Laundry treatment compositions |
WO2006002643A2 (en) | 2004-07-05 | 2006-01-12 | Novozymes A/S | Alpha-amylase variants with altered properties |
US20060073193A1 (en) | 2004-09-27 | 2006-04-06 | Novozymes A/S | Enzyme granules |
WO2006034710A1 (en) | 2004-09-27 | 2006-04-06 | Novozymes A/S | Enzyme granules |
EP1705241A1 (en) | 2005-03-23 | 2006-09-27 | Unilever N.V. | Detergent compositions in tablet form |
WO2007001262A1 (en) | 2005-06-17 | 2007-01-04 | The Procter & Gamble Company | Organic catalyst with enhanced enzyme compatibility |
WO2007044968A2 (en) | 2005-10-12 | 2007-04-19 | Genencor International, Inc. | Stable, durable granules with active agents |
WO2007087259A2 (en) | 2006-01-23 | 2007-08-02 | The Procter & Gamble Company | Enzyme and photobleach containing compositions |
WO2007087243A2 (en) | 2006-01-23 | 2007-08-02 | The Procter & Gamble Company | Detergent compositions |
WO2007087242A2 (en) | 2006-01-23 | 2007-08-02 | The Procter & Gamble Company | A composition comprising a lipase and a bleach catalyst |
WO2007087508A2 (en) | 2006-01-23 | 2007-08-02 | Novozymes A/S | Lipase variants |
WO2007087244A2 (en) | 2006-01-23 | 2007-08-02 | The Procter & Gamble Company | Detergent compositions |
WO2007087257A2 (en) | 2006-01-23 | 2007-08-02 | The Procter & Gamble Company | Enzyme and fabric hueing agent containing compositions |
WO2007087258A2 (en) | 2006-01-23 | 2007-08-02 | The Procter & Gamble Company | A composition comprising a lipase and a bleach catalyst |
EP1876226A1 (en) | 2006-07-07 | 2008-01-09 | The Procter and Gamble Company | Detergent compositions |
WO2009000605A1 (en) | 2007-06-22 | 2008-12-31 | Unilever N.V. | Granular enzymatic detergent compositions |
WO2009004295A1 (en) | 2007-07-05 | 2009-01-08 | Reckitt Benckiser N.V. | Laundry cleaning product |
WO2009004294A1 (en) | 2007-07-05 | 2009-01-08 | Reckitt Benckiser N.V. | Laundry cleaning product |
WO2009010375A1 (en) | 2007-07-16 | 2009-01-22 | Unilever Plc | A solid detergent composition |
WO2009015951A1 (en) | 2007-07-31 | 2009-02-05 | Henkel Ag & Co. Kgaa | Compositions comprising perhydrolases and alkylene glycol diacetates |
WO2009021813A2 (en) | 2007-08-10 | 2009-02-19 | Henkel Ag & Co. Kgaa | Washing or cleaning agent having polyester-based soil-release polymer |
WO2009021784A1 (en) | 2007-08-14 | 2009-02-19 | Unilever N.V. | Detergent tablet |
WO2009024780A1 (en) | 2007-08-20 | 2009-02-26 | Reckitt Benckiser N.V. | Detergent composition |
WO2009030632A1 (en) | 2007-09-04 | 2009-03-12 | Henkel Ag & Co. Kgaa | Polycyclic compounds as enzyme stabilizers |
WO2009040544A1 (en) | 2007-09-28 | 2009-04-02 | Reckitt Benckiser N.V. | Detergent composition |
WO2009040545A1 (en) | 2007-09-26 | 2009-04-02 | Reckitt Benckiser N.V. | Composition |
WO2009047126A2 (en) | 2007-10-12 | 2009-04-16 | Unilever Plc | Laundry detergent with pretreatment additive and its use |
WO2009047125A1 (en) | 2007-10-12 | 2009-04-16 | Unilever Plc | Improved visual cues for perfumed laundry detergents |
WO2009047127A1 (en) | 2007-10-12 | 2009-04-16 | Unilever Plc | Granular detergent compositions with contrasting lamellar visual cues |
WO2009047128A1 (en) | 2007-10-12 | 2009-04-16 | Unilever Plc | Performance ingredients in film particles |
WO2009050026A2 (en) | 2007-10-17 | 2009-04-23 | Unilever Nv | Laundry compositions |
WO2009063355A1 (en) | 2007-11-13 | 2009-05-22 | The Procter & Gamble Company | Process for creating a unit dose product with a printed water soluble material |
WO2009065770A1 (en) | 2007-11-21 | 2009-05-28 | Henkel Ag & Co. Kgaa | Granulate of a sensitive ingredient of a washing or cleaning agent |
WO2009068501A1 (en) | 2007-11-28 | 2009-06-04 | Henkel Ag & Co. Kgaa | Washing agent having stabilized enzymes |
WO2009072069A1 (en) | 2007-12-05 | 2009-06-11 | The Procter & Gamble Company | Package comprising detergent |
WO2009074403A1 (en) | 2007-12-11 | 2009-06-18 | Henkel Ag & Co. Kgaa | Cleaning agent |
WO2009074398A1 (en) | 2007-12-10 | 2009-06-18 | Henkel Ag & Co. Kgaa | Cleaning agent |
WO2009087033A1 (en) | 2008-01-10 | 2009-07-16 | Unilever Plc | Granules |
WO2009092699A1 (en) | 2008-01-24 | 2009-07-30 | Unilever Nv | Machine dishwash detergent compositions |
WO2009095645A1 (en) | 2008-01-28 | 2009-08-06 | Reckitt Benckiser N.V. | Composition |
WO2009102854A1 (en) | 2008-02-15 | 2009-08-20 | The Procter & Gamble Company | Cleaning compositions |
WO2009103822A1 (en) | 2008-04-01 | 2009-08-27 | Unilever Nv | Preparation of free flowing granules of methyglycine diacetic acid |
WO2009109500A1 (en) | 2008-02-29 | 2009-09-11 | Novozymes A/S | Polypeptides having lipase activity and polynucleotides encoding same |
WO2009112296A1 (en) | 2008-03-14 | 2009-09-17 | Unilever Plc | Laundry treatment compositions |
WO2009112298A1 (en) | 2008-03-14 | 2009-09-17 | Unilever Plc | Laundry treatment composition comprising polymeric lubricants |
WO2009117340A1 (en) | 2008-03-18 | 2009-09-24 | The Procter & Gamble Company | Detergent composition comprising a co-polyester of dicarboxylic acids and diols |
WO2009117342A1 (en) | 2008-03-18 | 2009-09-24 | The Procter & Gamble Company | A laundry detergent composition comprising the magnesium salt of ethylene diamine-n'n'-disuccinic acid |
WO2009117341A1 (en) | 2008-03-18 | 2009-09-24 | The Procter & Gamble Company | Detergent composition comprising cellulosic polymer |
WO2009115392A1 (en) | 2008-03-18 | 2009-09-24 | Henkel Ag & Co. Kgaa | Imidazolium salts as enzyme stabilizers |
WO2009115391A1 (en) | 2008-03-18 | 2009-09-24 | Henkel Ag & Co. Kgaa | Use of imidazolium salts in detergents and cleaning products |
WO2009124162A1 (en) | 2008-04-02 | 2009-10-08 | The Procter & Gamble Company | Detergent composition comprising non-ionic detersive surfactant and reactive dye |
WO2009121757A2 (en) | 2008-04-04 | 2009-10-08 | Unilever Plc | A novel personal wash bar |
WO2009121725A1 (en) | 2008-04-02 | 2009-10-08 | Henkel Ag & Co. Kgaa | Detergents and cleaners comprising proteases from xanthomonas |
WO2009122125A1 (en) | 2008-04-01 | 2009-10-08 | Reckitt Benckiser Inc. | Laundry treatment compositions |
WO2009124163A1 (en) | 2008-04-02 | 2009-10-08 | The Procter & Gamble Company | Detergent composition comprising reactive dye |
WO2009132870A1 (en) | 2008-05-02 | 2009-11-05 | Unilever Plc | Reduced spotting granules |
WO2010000636A1 (en) | 2008-07-03 | 2010-01-07 | Henkel Ag & Co. Kgaa | Solid fabric care composition with a polysaccharide |
WO2010003783A1 (en) | 2008-07-11 | 2010-01-14 | Unilever Nv | Copolymers and detergent compositions |
WO2010003792A1 (en) | 2008-07-09 | 2010-01-14 | Unilever Plc | Laundry compositions |
WO2010014395A1 (en) | 2008-07-28 | 2010-02-04 | The Procter & Gamble Company | Process for preparing a detergent composition |
WO2010018043A1 (en) | 2008-08-14 | 2010-02-18 | Unilever Nv | Builder composition |
WO2010024469A1 (en) | 2008-09-01 | 2010-03-04 | The Procter & Gamble Company | Hydrophobic group-containing copolymer and process for the production thereof |
WO2010024470A1 (en) | 2008-09-01 | 2010-03-04 | The Procter & Gamble Company | Composition comprising polyoxyalkylene-based polymer composition |
WO2010024467A1 (en) | 2008-09-01 | 2010-03-04 | The Procter & Gamble Company | Polymer composition and process for the production thereof |
WO2010025161A1 (en) | 2008-08-27 | 2010-03-04 | The Procter & Gamble Company | A detergent composition comprising carbohydrate:acceptor oxidoreductase |
WO2010030541A1 (en) | 2008-09-12 | 2010-03-18 | The Procter & Gamble Company | Laundry particle made by extrusion comprising a hueing dye |
WO2010030539A1 (en) | 2008-09-12 | 2010-03-18 | The Procter & Gamble Company | Laundry particle made by extrusion comprising a hueing dye and fatty acid soap |
WO2010030540A1 (en) | 2008-09-12 | 2010-03-18 | The Procter & Gamble Company | Particles comprising a hueing dye |
WO2010033979A2 (en) | 2008-09-22 | 2010-03-25 | The Procter & Gamble Company | Specific polybranched polyaldehydes, polyalcohols, and surfactants and consumer products based thereon |
WO2010033746A1 (en) | 2008-09-19 | 2010-03-25 | The Procter & Gamble Company | Detergent composition containing suds boosting and suds stabilizing modified biopolymer |
WO2010031607A1 (en) | 2008-09-18 | 2010-03-25 | Henkel Ag & Co. Kgaa | Bleach-containing cleaning agent |
WO2010033747A1 (en) | 2008-09-19 | 2010-03-25 | The Procter & Gamble Company | Dual character biopolymer useful in cleaning products |
WO2010044905A2 (en) | 2008-04-02 | 2010-04-22 | The Procter & Gamble Company | A kit of parts comprising a solid laundry detergent composition and a dosing device |
WO2010049187A1 (en) | 2008-10-31 | 2010-05-06 | Henkel Ag & Co. Kgaa | Dishwasher detergent |
WO2010054986A1 (en) | 2008-11-12 | 2010-05-20 | Unilever Plc | Fabric whiteness measurement system |
WO2010057784A1 (en) | 2008-11-20 | 2010-05-27 | Unilever Plc | Fabric whiteness measurement system |
WO2010060821A2 (en) | 2008-11-27 | 2010-06-03 | Henkel Ag & Co. Kgaa | Detergents and cleaning agents containing proteases from bacillus pumilus |
WO2010063689A1 (en) | 2008-12-05 | 2010-06-10 | Henkel Ag & Co. Kgaa | Automatic dishwashing detergent tablets |
WO2010066631A1 (en) | 2008-12-12 | 2010-06-17 | Henkel Ag & Co. Kgaa | Laundry article having cleaning and conditioning properties |
WO2010066486A2 (en) | 2008-12-09 | 2010-06-17 | Henkel Ag & Co. Kgaa | Photolabile fragrance storage substances |
WO2010066632A1 (en) | 2008-12-12 | 2010-06-17 | Henkel Ag & Co. Kgaa | Laundry article having cleaning and conditioning properties |
WO2010069905A1 (en) | 2008-12-19 | 2010-06-24 | Henkel Ag & Co. Kgaa | Dishwasher detergent |
WO2010069718A1 (en) | 2008-12-16 | 2010-06-24 | Unilever Nv | Solid builder composition |
WO2010069957A1 (en) | 2008-12-17 | 2010-06-24 | Unilever Plc | Laundry detergent composition |
WO2010069742A1 (en) | 2008-12-18 | 2010-06-24 | Unilever Nv | Laundry detergent composition |
WO2010072603A1 (en) | 2008-12-15 | 2010-07-01 | Henkel Ag & Co. Kgaa | Dishwasher detergent |
WO2010072456A1 (en) | 2008-12-23 | 2010-07-01 | Henkel Ag & Co. Kgaa | Use of star-shaped polymers having peripheral negatively charged groups and/or peripheral silyl groups for finishing surfaces |
WO2010076165A1 (en) | 2008-12-15 | 2010-07-08 | Henkel Ag & Co. Kgaa | Machine dishwashing detergent |
WO2010076292A1 (en) | 2008-12-29 | 2010-07-08 | Unilever Plc | Structured aqueous detergent compositions |
WO2010078979A1 (en) | 2009-01-09 | 2010-07-15 | Henkel Ag & Co. Kgaa | Color-protecting dishwasher detergent |
WO2010084039A1 (en) | 2009-01-26 | 2010-07-29 | Unilever Plc | Incorporation of dye into granular laundry composition |
WO2010084203A1 (en) | 2009-01-26 | 2010-07-29 | Henkel Ag & Co. Kgaa | Additional laundry item |
WO2010090915A1 (en) | 2009-02-09 | 2010-08-12 | The Procter & Gamble Company | Detergent composition |
WO2010094356A1 (en) | 2009-02-18 | 2010-08-26 | Henkel Ag & Co. Kgaa | Pro-fragrance copolymeric compounds |
WO2010099997A1 (en) | 2009-03-05 | 2010-09-10 | Unilever Plc | Dye radical initiators |
WO2010102861A1 (en) | 2009-03-12 | 2010-09-16 | Unilever Plc | Dye-polymers formulations |
WO2010107635A1 (en) | 2009-03-16 | 2010-09-23 | The Procter & Gamble Company | Method of industrial or institutional laundry for a polyester load |
WO2010108000A1 (en) | 2009-03-18 | 2010-09-23 | The Procter & Gamble Company | Structured fluid detergent compositions comprising dibenzylidene polyol acetal derivatives and detersive enzymes |
WO2010105962A1 (en) | 2009-03-20 | 2010-09-23 | Henkel Ag & Co. Kgaa | Detergent or cleaning agent comprising a bleach-boosting transition metal complex which is optionally produced in situ |
WO2010105942A1 (en) | 2009-03-20 | 2010-09-23 | Henkel Ag & Co. Kgaa | 4-aminopyridine derivatives as catalysts for the cleavage of organic esters |
WO2010108002A1 (en) | 2009-03-18 | 2010-09-23 | The Procter & Gamble Company | Structured fluid detergent compositions comprising dibenzylidene sorbitol acetal derivatives |
WO2010105961A1 (en) | 2009-03-20 | 2010-09-23 | Henkel Ag & Co. Kgaa | Detergent or cleaning agent comprising a bleach-boosting transition metal complex which is optionally produced in situ |
WO2010111365A1 (en) | 2009-03-26 | 2010-09-30 | The Procter & Gamble Company | A perfume encapsulate, a laundry detergent composition comprising a perfume encapsulate, and a process for preparing a perfume encapsulate |
WO2010115813A1 (en) | 2009-04-07 | 2010-10-14 | Henkel Ag & Co. Kgaa | Use of a prebiotically effective surfactant combination |
WO2010120863A1 (en) | 2009-04-17 | 2010-10-21 | The Procter & Gamble Company | Fabric care compositions comprising organosiloxane polymers |
WO2010118959A1 (en) | 2009-04-15 | 2010-10-21 | Henkel Ag & Co. Kgaa | Granular washing, cleaning or treatment agent additive |
WO2010122051A1 (en) | 2009-04-24 | 2010-10-28 | Unilever Plc | High active detergent particles |
WO2010135238A1 (en) | 2009-05-19 | 2010-11-25 | The Procter & Gamble Company | A method for printing water-soluble film |
WO2010142503A1 (en) | 2009-06-12 | 2010-12-16 | Unilever Plc | Cationic dye polymers |
WO2010142539A1 (en) | 2009-06-08 | 2010-12-16 | Henkel Ag & Co. Kgaa | Nanoparticulate manganese dioxide |
WO2010145887A1 (en) | 2009-06-15 | 2010-12-23 | Unilever Plc | Anionic dye polymers |
WO2011005905A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | A mildly alkaline, low-built, solid fabric treatment detergent composition comprising phthalimido peroxy caproic acid |
WO2011005904A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Detergent composition |
WO2011005730A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | A catalytic laundry detergent composition comprising relatively low levels of water-soluble electrolyte |
WO2011005912A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Method of laundering fabric |
WO2011005803A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Continuous process for making a laundry detergent composition |
WO2011005910A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Method of laundering fabric using a compacted laundry detergent composition |
WO2011005630A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Method of laundering fabric using a compacted laundry detergent composition |
WO2011005830A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Laundry detergent composition comprising low level of sulphate |
WO2011005844A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Method of laundering fabric using a compacted laundry detergent composition |
WO2011005623A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Laundry detergent composition comprising low level of bleach |
WO2011005813A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Method of laundering fabric using a compacted laundry detergent composition |
WO2011016958A2 (en) | 2009-07-27 | 2011-02-10 | The Procter & Gamble Company | Detergent composition |
WO2011025615A2 (en) | 2009-08-13 | 2011-03-03 | The Procter & Gamble Company | Method of laundering fabrics at low temperature |
WO2011023716A1 (en) | 2009-08-26 | 2011-03-03 | Henkel Ag & Co. Kgaa | Improved washing performance using radical traps |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5858117A (en) * | 1994-08-31 | 1999-01-12 | Ecolab Inc. | Proteolytic enzyme cleaner |
JP3081534B2 (en) * | 1995-12-22 | 2000-08-28 | 花王株式会社 | Enzyme-containing granules, method for producing the same, and compositions containing the same |
US6046149A (en) * | 1996-04-17 | 2000-04-04 | Procter & Gamble Company | Detergent compositions |
DE19824687A1 (en) * | 1998-06-03 | 1999-12-09 | Henkel Kgaa | Detergents and cleaning agents containing amylase and acetonitrile derivatives |
US6268329B1 (en) | 1998-06-30 | 2001-07-31 | Nouozymes A/S | Enzyme containing granule |
DE19844522A1 (en) * | 1998-09-29 | 2000-03-30 | Henkel Kgaa | Granulation process |
AU7405400A (en) * | 1999-10-01 | 2001-05-10 | Novozymes A/S | Enzyme granulate |
GB2374082A (en) * | 2001-04-04 | 2002-10-09 | Procter & Gamble | Particles for a detergent product |
EP1698687A1 (en) * | 2005-02-07 | 2006-09-06 | The Procter & Gamble Company | Detergent compositions |
KR101457834B1 (en) | 2005-08-31 | 2014-11-05 | 아브락시스 바이오사이언스, 엘엘씨 | Compositions and methods for preparation of poorly water soluble drugs with increased stability |
PL1903098T3 (en) * | 2006-07-27 | 2009-04-30 | Evonik Treibacher Gmbh | Coated sodium percarbonate particle |
SI1882732T1 (en) * | 2006-07-27 | 2010-08-31 | Evonik Degussa Gmbh | Coated particles of sodium percarbonate |
KR20100123694A (en) * | 2008-02-14 | 2010-11-24 | 다니스코 유에스 인크. | Small enzyme-containing granules |
-
2011
- 2011-04-15 BR BR112012024674-7A patent/BR112012024674B1/en active IP Right Grant
- 2011-04-15 JP JP2013506580A patent/JP5944887B2/en active Active
- 2011-04-15 EP EP11715914.5A patent/EP2563910B1/en not_active Not-in-force
- 2011-04-15 PL PL14187309T patent/PL2840134T3/en unknown
- 2011-04-15 MX MX2012012096A patent/MX2012012096A/en active IP Right Grant
- 2011-04-15 MX MX2015013675A patent/MX349735B/en unknown
- 2011-04-15 EP EP14187309.1A patent/EP2840134B1/en active Active
- 2011-04-15 CN CN201180025872.8A patent/CN102906251B/en active Active
- 2011-04-15 KR KR1020127030043A patent/KR101904484B1/en active IP Right Grant
- 2011-04-15 EP EP17187533.9A patent/EP3279319B1/en active Active
- 2011-04-15 WO PCT/EP2011/056053 patent/WO2011134809A1/en active Application Filing
- 2011-04-15 RU RU2012150279/10A patent/RU2573907C2/en active
- 2011-04-15 CN CN201610849442.2A patent/CN106978403B/en active Active
- 2011-04-15 AU AU2011246662A patent/AU2011246662B2/en not_active Ceased
- 2011-04-15 ES ES14187309.1T patent/ES2646166T3/en active Active
- 2011-04-15 CA CA2797032A patent/CA2797032A1/en not_active Abandoned
- 2011-04-15 US US13/643,008 patent/US9107433B2/en active Active
-
2012
- 2012-10-12 ZA ZA2012/07687A patent/ZA201207687B/en unknown
Patent Citations (184)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1296839A (en) | 1969-05-29 | 1972-11-22 | ||
US4435307A (en) | 1980-04-30 | 1984-03-06 | Novo Industri A/S | Detergent cellulase |
WO1989006270A1 (en) | 1988-01-07 | 1989-07-13 | Novo-Nordisk A/S | Enzymatic detergent |
WO1989006279A1 (en) | 1988-01-07 | 1989-07-13 | Novo-Nordisk A/S | Mutated subtilisin genes |
WO1991017243A1 (en) | 1990-05-09 | 1991-11-14 | Novo Nordisk A/S | A cellulase preparation comprising an endoglucanase enzyme |
WO1991017244A1 (en) | 1990-05-09 | 1991-11-14 | Novo Nordisk A/S | An enzyme capable of degrading cellulose or hemicellulose |
WO1992005249A1 (en) | 1990-09-13 | 1992-04-02 | Novo Nordisk A/S | Lipase variants |
EP0495257A1 (en) | 1991-01-16 | 1992-07-22 | The Procter & Gamble Company | Compact detergent compositions with high activity cellulase |
WO1992019729A1 (en) | 1991-05-01 | 1992-11-12 | Novo Nordisk A/S | Stabilized enzymes and detergent compositions |
WO1994002597A1 (en) | 1992-07-23 | 1994-02-03 | Novo Nordisk A/S | MUTANT α-AMYLASE, DETERGENT, DISH WASHING AGENT, AND LIQUEFACTION AGENT |
WO1994007998A1 (en) | 1992-10-06 | 1994-04-14 | Novo Nordisk A/S | Cellulase variants |
WO1994018314A1 (en) | 1993-02-11 | 1994-08-18 | Genencor International, Inc. | Oxidatively stable alpha-amylase |
WO1994025583A1 (en) | 1993-05-05 | 1994-11-10 | Novo Nordisk A/S | A recombinant trypsin-like protease |
WO1995010603A1 (en) | 1993-10-08 | 1995-04-20 | Novo Nordisk A/S | Amylase variants |
WO1995026397A1 (en) | 1994-03-29 | 1995-10-05 | Novo Nordisk A/S | Alkaline bacillus amylase |
WO1996023873A1 (en) | 1995-02-03 | 1996-08-08 | Novo Nordisk A/S | Amylase variants |
WO1996029397A1 (en) | 1995-03-17 | 1996-09-26 | Novo Nordisk A/S | Novel endoglucanases |
US5977053A (en) | 1995-07-31 | 1999-11-02 | Bayer Ag | Detergents and cleaners containing iminodisuccinates |
WO1997007202A1 (en) | 1995-08-11 | 1997-02-27 | Novo Nordisk A/S | Novel lipolytic enzymes |
WO1997043424A1 (en) | 1996-05-14 | 1997-11-20 | Genencor International, Inc. | MODIFIED α-AMYLASES HAVING ALTERED CALCIUM BINDING PROPERTIES |
WO1998012307A1 (en) | 1996-09-17 | 1998-03-26 | Novo Nordisk A/S | Cellulase variants |
WO1998017767A1 (en) | 1996-10-18 | 1998-04-30 | The Procter & Gamble Company | Detergent compositions |
WO1998020116A1 (en) | 1996-11-04 | 1998-05-14 | Novo Nordisk A/S | Subtilase variants and compositions |
WO1998020115A1 (en) | 1996-11-04 | 1998-05-14 | Novo Nordisk A/S | Subtilase variants and compositions |
WO1998034946A1 (en) | 1997-02-12 | 1998-08-13 | Massachusetts Institute Of Technology | Daxx, a novel fas-binding protein that activates jnk and apoptosis |
WO1999002663A1 (en) | 1997-07-07 | 1999-01-21 | Novo Nordisk A/S | Alkaline xyloglucanase |
WO1999027084A1 (en) | 1997-11-24 | 1999-06-03 | Novo Nordisk A/S | Novel pectate lyases |
US6124127A (en) | 1997-11-24 | 2000-09-26 | Novo Nordisk A/S | Pectate lyase |
WO1999027083A1 (en) | 1997-11-24 | 1999-06-03 | Novo Nordisk A/S | PECTIN DEGRADING ENZYMES FROM $i(BACILLUS LICHENIFORMIS) |
WO1999032595A1 (en) | 1997-12-20 | 1999-07-01 | Genencor International, Inc. | Granule with hydrated barrier material |
WO1999037746A1 (en) | 1998-01-26 | 1999-07-29 | The Procter & Gamble Company | Multi-layer detergent tablet |
WO1999064619A2 (en) | 1998-06-10 | 1999-12-16 | Novozymes A/S | Novel mannanases |
WO2000001793A1 (en) | 1998-06-30 | 2000-01-13 | Novozymes A/S | A new improved enzyme containing granule |
US6472364B1 (en) | 1998-10-13 | 2002-10-29 | The Procter & Gamble Company | Detergent compositions or components |
WO2000032758A1 (en) | 1998-11-27 | 2000-06-08 | Novozymes A/S | Lipolytic enzyme variants |
JP2000210081A (en) | 1999-01-21 | 2000-08-02 | Kao Corp | Heat-resistant alkali cellulase gene |
WO2000060060A2 (en) | 1999-03-31 | 2000-10-12 | Novozymes A/S | Polypeptides having alkaline alpha-amylase activity and nucleic acids encoding same |
WO2000060063A1 (en) | 1999-03-31 | 2000-10-12 | Novozymes A/S | Lipase variant |
WO2001062903A1 (en) | 2000-02-24 | 2001-08-30 | Novozymes A/S | Family 44 xyloglucanases |
WO2001066712A2 (en) | 2000-03-08 | 2001-09-13 | Novozymes A/S | Variants with altered properties |
WO2002006442A2 (en) | 2000-07-19 | 2002-01-24 | Novozymes A/S | Cell-wall degrading enzyme variants |
WO2002055679A2 (en) | 2001-01-10 | 2002-07-18 | Novozymes A/S | Thermostable lipolytic enzyme variant |
WO2002092741A2 (en) | 2001-05-14 | 2002-11-21 | Novozymes A/S | 0etergent compositions comprising bacillus subtilis pectate lyases |
WO2002099091A2 (en) | 2001-06-06 | 2002-12-12 | Novozymes A/S | Endo-beta-1,4-glucanase from bacillus |
WO2003000456A2 (en) | 2001-06-22 | 2003-01-03 | Konrad Seppelt | Method for carrying out local laser-induced etching of solid materials |
WO2003055967A1 (en) * | 2001-12-21 | 2003-07-10 | Novozymes A/S | Salt coatings |
US20060247149A1 (en) * | 2001-12-21 | 2006-11-02 | Novozymes A/S | Salt coatings |
WO2003095638A1 (en) | 2002-05-14 | 2003-11-20 | Novozymes A/S | Pectate lyase variants |
EP1382668A1 (en) | 2002-06-11 | 2004-01-21 | Unilever N.V. | Detergent tablets |
US20040033927A1 (en) | 2002-07-01 | 2004-02-19 | Novozymes A/S | Stabilization of granules |
WO2004003188A2 (en) | 2002-07-01 | 2004-01-08 | Novozymes A/S | Stabilization of granules |
WO2004053039A2 (en) | 2002-12-11 | 2004-06-24 | Novozymes A/S | Detergent composition comprising endo-glucanase |
WO2004067739A2 (en) | 2003-01-27 | 2004-08-12 | Novozymes A/S | Stabilization of granules |
WO2004074419A2 (en) | 2003-02-18 | 2004-09-02 | Novozymes A/S | Detergent compositions |
WO2004099400A2 (en) | 2003-05-09 | 2004-11-18 | Novozymes A/S | Variant lipolytic ensymes |
WO2005003274A1 (en) | 2003-06-18 | 2005-01-13 | Unilever Plc | Laundry treatment compositions |
WO2005003276A1 (en) | 2003-06-18 | 2005-01-13 | Unilever Plc | Laundry treatment compositions |
WO2005003275A1 (en) | 2003-06-18 | 2005-01-13 | Unilever Plc | Laundry treatment compositions |
WO2006002643A2 (en) | 2004-07-05 | 2006-01-12 | Novozymes A/S | Alpha-amylase variants with altered properties |
US20060073193A1 (en) | 2004-09-27 | 2006-04-06 | Novozymes A/S | Enzyme granules |
WO2006034710A1 (en) | 2004-09-27 | 2006-04-06 | Novozymes A/S | Enzyme granules |
EP1705241A1 (en) | 2005-03-23 | 2006-09-27 | Unilever N.V. | Detergent compositions in tablet form |
WO2007001262A1 (en) | 2005-06-17 | 2007-01-04 | The Procter & Gamble Company | Organic catalyst with enhanced enzyme compatibility |
WO2007044968A2 (en) | 2005-10-12 | 2007-04-19 | Genencor International, Inc. | Stable, durable granules with active agents |
WO2007087258A2 (en) | 2006-01-23 | 2007-08-02 | The Procter & Gamble Company | A composition comprising a lipase and a bleach catalyst |
WO2007087243A2 (en) | 2006-01-23 | 2007-08-02 | The Procter & Gamble Company | Detergent compositions |
WO2007087242A2 (en) | 2006-01-23 | 2007-08-02 | The Procter & Gamble Company | A composition comprising a lipase and a bleach catalyst |
WO2007087508A2 (en) | 2006-01-23 | 2007-08-02 | Novozymes A/S | Lipase variants |
WO2007087244A2 (en) | 2006-01-23 | 2007-08-02 | The Procter & Gamble Company | Detergent compositions |
WO2007087257A2 (en) | 2006-01-23 | 2007-08-02 | The Procter & Gamble Company | Enzyme and fabric hueing agent containing compositions |
WO2007087259A2 (en) | 2006-01-23 | 2007-08-02 | The Procter & Gamble Company | Enzyme and photobleach containing compositions |
EP1876226A1 (en) | 2006-07-07 | 2008-01-09 | The Procter and Gamble Company | Detergent compositions |
WO2009000605A1 (en) | 2007-06-22 | 2008-12-31 | Unilever N.V. | Granular enzymatic detergent compositions |
WO2009004295A1 (en) | 2007-07-05 | 2009-01-08 | Reckitt Benckiser N.V. | Laundry cleaning product |
WO2009004294A1 (en) | 2007-07-05 | 2009-01-08 | Reckitt Benckiser N.V. | Laundry cleaning product |
WO2009010375A1 (en) | 2007-07-16 | 2009-01-22 | Unilever Plc | A solid detergent composition |
WO2009015951A1 (en) | 2007-07-31 | 2009-02-05 | Henkel Ag & Co. Kgaa | Compositions comprising perhydrolases and alkylene glycol diacetates |
WO2009021813A2 (en) | 2007-08-10 | 2009-02-19 | Henkel Ag & Co. Kgaa | Washing or cleaning agent having polyester-based soil-release polymer |
WO2009021784A1 (en) | 2007-08-14 | 2009-02-19 | Unilever N.V. | Detergent tablet |
WO2009024780A1 (en) | 2007-08-20 | 2009-02-26 | Reckitt Benckiser N.V. | Detergent composition |
WO2009030632A1 (en) | 2007-09-04 | 2009-03-12 | Henkel Ag & Co. Kgaa | Polycyclic compounds as enzyme stabilizers |
WO2009040545A1 (en) | 2007-09-26 | 2009-04-02 | Reckitt Benckiser N.V. | Composition |
WO2009040544A1 (en) | 2007-09-28 | 2009-04-02 | Reckitt Benckiser N.V. | Detergent composition |
WO2009047125A1 (en) | 2007-10-12 | 2009-04-16 | Unilever Plc | Improved visual cues for perfumed laundry detergents |
WO2009047126A2 (en) | 2007-10-12 | 2009-04-16 | Unilever Plc | Laundry detergent with pretreatment additive and its use |
WO2009047127A1 (en) | 2007-10-12 | 2009-04-16 | Unilever Plc | Granular detergent compositions with contrasting lamellar visual cues |
WO2009047128A1 (en) | 2007-10-12 | 2009-04-16 | Unilever Plc | Performance ingredients in film particles |
WO2009050026A2 (en) | 2007-10-17 | 2009-04-23 | Unilever Nv | Laundry compositions |
WO2009063355A1 (en) | 2007-11-13 | 2009-05-22 | The Procter & Gamble Company | Process for creating a unit dose product with a printed water soluble material |
WO2009065770A1 (en) | 2007-11-21 | 2009-05-28 | Henkel Ag & Co. Kgaa | Granulate of a sensitive ingredient of a washing or cleaning agent |
WO2009068501A1 (en) | 2007-11-28 | 2009-06-04 | Henkel Ag & Co. Kgaa | Washing agent having stabilized enzymes |
WO2009072069A1 (en) | 2007-12-05 | 2009-06-11 | The Procter & Gamble Company | Package comprising detergent |
WO2009074398A1 (en) | 2007-12-10 | 2009-06-18 | Henkel Ag & Co. Kgaa | Cleaning agent |
WO2009074403A1 (en) | 2007-12-11 | 2009-06-18 | Henkel Ag & Co. Kgaa | Cleaning agent |
WO2009087033A1 (en) | 2008-01-10 | 2009-07-16 | Unilever Plc | Granules |
WO2009092699A1 (en) | 2008-01-24 | 2009-07-30 | Unilever Nv | Machine dishwash detergent compositions |
WO2009095645A1 (en) | 2008-01-28 | 2009-08-06 | Reckitt Benckiser N.V. | Composition |
WO2009102854A1 (en) | 2008-02-15 | 2009-08-20 | The Procter & Gamble Company | Cleaning compositions |
WO2009109500A1 (en) | 2008-02-29 | 2009-09-11 | Novozymes A/S | Polypeptides having lipase activity and polynucleotides encoding same |
WO2009112296A1 (en) | 2008-03-14 | 2009-09-17 | Unilever Plc | Laundry treatment compositions |
WO2009112298A1 (en) | 2008-03-14 | 2009-09-17 | Unilever Plc | Laundry treatment composition comprising polymeric lubricants |
WO2009115391A1 (en) | 2008-03-18 | 2009-09-24 | Henkel Ag & Co. Kgaa | Use of imidazolium salts in detergents and cleaning products |
WO2009117340A1 (en) | 2008-03-18 | 2009-09-24 | The Procter & Gamble Company | Detergent composition comprising a co-polyester of dicarboxylic acids and diols |
WO2009117342A1 (en) | 2008-03-18 | 2009-09-24 | The Procter & Gamble Company | A laundry detergent composition comprising the magnesium salt of ethylene diamine-n'n'-disuccinic acid |
WO2009117341A1 (en) | 2008-03-18 | 2009-09-24 | The Procter & Gamble Company | Detergent composition comprising cellulosic polymer |
WO2009115392A1 (en) | 2008-03-18 | 2009-09-24 | Henkel Ag & Co. Kgaa | Imidazolium salts as enzyme stabilizers |
WO2009103822A1 (en) | 2008-04-01 | 2009-08-27 | Unilever Nv | Preparation of free flowing granules of methyglycine diacetic acid |
WO2009122125A1 (en) | 2008-04-01 | 2009-10-08 | Reckitt Benckiser Inc. | Laundry treatment compositions |
WO2009124162A1 (en) | 2008-04-02 | 2009-10-08 | The Procter & Gamble Company | Detergent composition comprising non-ionic detersive surfactant and reactive dye |
WO2009121725A1 (en) | 2008-04-02 | 2009-10-08 | Henkel Ag & Co. Kgaa | Detergents and cleaners comprising proteases from xanthomonas |
WO2009124163A1 (en) | 2008-04-02 | 2009-10-08 | The Procter & Gamble Company | Detergent composition comprising reactive dye |
WO2010044905A2 (en) | 2008-04-02 | 2010-04-22 | The Procter & Gamble Company | A kit of parts comprising a solid laundry detergent composition and a dosing device |
WO2009121757A2 (en) | 2008-04-04 | 2009-10-08 | Unilever Plc | A novel personal wash bar |
WO2009132870A1 (en) | 2008-05-02 | 2009-11-05 | Unilever Plc | Reduced spotting granules |
WO2010000636A1 (en) | 2008-07-03 | 2010-01-07 | Henkel Ag & Co. Kgaa | Solid fabric care composition with a polysaccharide |
WO2010003792A1 (en) | 2008-07-09 | 2010-01-14 | Unilever Plc | Laundry compositions |
WO2010003783A1 (en) | 2008-07-11 | 2010-01-14 | Unilever Nv | Copolymers and detergent compositions |
WO2010014395A1 (en) | 2008-07-28 | 2010-02-04 | The Procter & Gamble Company | Process for preparing a detergent composition |
WO2010018043A1 (en) | 2008-08-14 | 2010-02-18 | Unilever Nv | Builder composition |
WO2010025161A1 (en) | 2008-08-27 | 2010-03-04 | The Procter & Gamble Company | A detergent composition comprising carbohydrate:acceptor oxidoreductase |
WO2010024470A1 (en) | 2008-09-01 | 2010-03-04 | The Procter & Gamble Company | Composition comprising polyoxyalkylene-based polymer composition |
WO2010024469A1 (en) | 2008-09-01 | 2010-03-04 | The Procter & Gamble Company | Hydrophobic group-containing copolymer and process for the production thereof |
WO2010024467A1 (en) | 2008-09-01 | 2010-03-04 | The Procter & Gamble Company | Polymer composition and process for the production thereof |
WO2010030541A1 (en) | 2008-09-12 | 2010-03-18 | The Procter & Gamble Company | Laundry particle made by extrusion comprising a hueing dye |
WO2010030539A1 (en) | 2008-09-12 | 2010-03-18 | The Procter & Gamble Company | Laundry particle made by extrusion comprising a hueing dye and fatty acid soap |
WO2010030540A1 (en) | 2008-09-12 | 2010-03-18 | The Procter & Gamble Company | Particles comprising a hueing dye |
WO2010031607A1 (en) | 2008-09-18 | 2010-03-25 | Henkel Ag & Co. Kgaa | Bleach-containing cleaning agent |
WO2010033747A1 (en) | 2008-09-19 | 2010-03-25 | The Procter & Gamble Company | Dual character biopolymer useful in cleaning products |
WO2010033746A1 (en) | 2008-09-19 | 2010-03-25 | The Procter & Gamble Company | Detergent composition containing suds boosting and suds stabilizing modified biopolymer |
WO2010033897A1 (en) | 2008-09-19 | 2010-03-25 | The Procter & Gamble Company | Cleaning composition containing substituted starch |
WO2010033976A2 (en) | 2008-09-22 | 2010-03-25 | The Procter & Gamble Company | Specific branched aldehydes, alcohols, surfactants and consumer products based thereon |
WO2010033979A2 (en) | 2008-09-22 | 2010-03-25 | The Procter & Gamble Company | Specific polybranched polyaldehydes, polyalcohols, and surfactants and consumer products based thereon |
WO2010049187A1 (en) | 2008-10-31 | 2010-05-06 | Henkel Ag & Co. Kgaa | Dishwasher detergent |
WO2010054986A1 (en) | 2008-11-12 | 2010-05-20 | Unilever Plc | Fabric whiteness measurement system |
WO2010057784A1 (en) | 2008-11-20 | 2010-05-27 | Unilever Plc | Fabric whiteness measurement system |
WO2010060821A2 (en) | 2008-11-27 | 2010-06-03 | Henkel Ag & Co. Kgaa | Detergents and cleaning agents containing proteases from bacillus pumilus |
WO2010063689A1 (en) | 2008-12-05 | 2010-06-10 | Henkel Ag & Co. Kgaa | Automatic dishwashing detergent tablets |
WO2010066486A2 (en) | 2008-12-09 | 2010-06-17 | Henkel Ag & Co. Kgaa | Photolabile fragrance storage substances |
WO2010066631A1 (en) | 2008-12-12 | 2010-06-17 | Henkel Ag & Co. Kgaa | Laundry article having cleaning and conditioning properties |
WO2010066632A1 (en) | 2008-12-12 | 2010-06-17 | Henkel Ag & Co. Kgaa | Laundry article having cleaning and conditioning properties |
WO2010072603A1 (en) | 2008-12-15 | 2010-07-01 | Henkel Ag & Co. Kgaa | Dishwasher detergent |
WO2010076165A1 (en) | 2008-12-15 | 2010-07-08 | Henkel Ag & Co. Kgaa | Machine dishwashing detergent |
WO2010069718A1 (en) | 2008-12-16 | 2010-06-24 | Unilever Nv | Solid builder composition |
WO2010069957A1 (en) | 2008-12-17 | 2010-06-24 | Unilever Plc | Laundry detergent composition |
WO2010069742A1 (en) | 2008-12-18 | 2010-06-24 | Unilever Nv | Laundry detergent composition |
WO2010069905A1 (en) | 2008-12-19 | 2010-06-24 | Henkel Ag & Co. Kgaa | Dishwasher detergent |
WO2010072456A1 (en) | 2008-12-23 | 2010-07-01 | Henkel Ag & Co. Kgaa | Use of star-shaped polymers having peripheral negatively charged groups and/or peripheral silyl groups for finishing surfaces |
WO2010076292A1 (en) | 2008-12-29 | 2010-07-08 | Unilever Plc | Structured aqueous detergent compositions |
WO2010078979A1 (en) | 2009-01-09 | 2010-07-15 | Henkel Ag & Co. Kgaa | Color-protecting dishwasher detergent |
WO2010084039A1 (en) | 2009-01-26 | 2010-07-29 | Unilever Plc | Incorporation of dye into granular laundry composition |
WO2010084203A1 (en) | 2009-01-26 | 2010-07-29 | Henkel Ag & Co. Kgaa | Additional laundry item |
WO2010090915A1 (en) | 2009-02-09 | 2010-08-12 | The Procter & Gamble Company | Detergent composition |
WO2010094356A1 (en) | 2009-02-18 | 2010-08-26 | Henkel Ag & Co. Kgaa | Pro-fragrance copolymeric compounds |
WO2010099997A1 (en) | 2009-03-05 | 2010-09-10 | Unilever Plc | Dye radical initiators |
WO2010102861A1 (en) | 2009-03-12 | 2010-09-16 | Unilever Plc | Dye-polymers formulations |
WO2010107635A1 (en) | 2009-03-16 | 2010-09-23 | The Procter & Gamble Company | Method of industrial or institutional laundry for a polyester load |
WO2010108000A1 (en) | 2009-03-18 | 2010-09-23 | The Procter & Gamble Company | Structured fluid detergent compositions comprising dibenzylidene polyol acetal derivatives and detersive enzymes |
WO2010108002A1 (en) | 2009-03-18 | 2010-09-23 | The Procter & Gamble Company | Structured fluid detergent compositions comprising dibenzylidene sorbitol acetal derivatives |
WO2010105961A1 (en) | 2009-03-20 | 2010-09-23 | Henkel Ag & Co. Kgaa | Detergent or cleaning agent comprising a bleach-boosting transition metal complex which is optionally produced in situ |
WO2010105942A1 (en) | 2009-03-20 | 2010-09-23 | Henkel Ag & Co. Kgaa | 4-aminopyridine derivatives as catalysts for the cleavage of organic esters |
WO2010105962A1 (en) | 2009-03-20 | 2010-09-23 | Henkel Ag & Co. Kgaa | Detergent or cleaning agent comprising a bleach-boosting transition metal complex which is optionally produced in situ |
WO2010111365A1 (en) | 2009-03-26 | 2010-09-30 | The Procter & Gamble Company | A perfume encapsulate, a laundry detergent composition comprising a perfume encapsulate, and a process for preparing a perfume encapsulate |
WO2010115813A1 (en) | 2009-04-07 | 2010-10-14 | Henkel Ag & Co. Kgaa | Use of a prebiotically effective surfactant combination |
WO2010118959A1 (en) | 2009-04-15 | 2010-10-21 | Henkel Ag & Co. Kgaa | Granular washing, cleaning or treatment agent additive |
WO2010120863A1 (en) | 2009-04-17 | 2010-10-21 | The Procter & Gamble Company | Fabric care compositions comprising organosiloxane polymers |
WO2010122051A1 (en) | 2009-04-24 | 2010-10-28 | Unilever Plc | High active detergent particles |
WO2010135238A1 (en) | 2009-05-19 | 2010-11-25 | The Procter & Gamble Company | A method for printing water-soluble film |
WO2010142539A1 (en) | 2009-06-08 | 2010-12-16 | Henkel Ag & Co. Kgaa | Nanoparticulate manganese dioxide |
WO2010142503A1 (en) | 2009-06-12 | 2010-12-16 | Unilever Plc | Cationic dye polymers |
WO2010145887A1 (en) | 2009-06-15 | 2010-12-23 | Unilever Plc | Anionic dye polymers |
WO2011005904A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Detergent composition |
WO2011005830A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Laundry detergent composition comprising low level of sulphate |
WO2011005730A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | A catalytic laundry detergent composition comprising relatively low levels of water-soluble electrolyte |
WO2011005912A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Method of laundering fabric |
WO2011005803A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Continuous process for making a laundry detergent composition |
WO2011005910A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Method of laundering fabric using a compacted laundry detergent composition |
WO2011005630A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Method of laundering fabric using a compacted laundry detergent composition |
WO2011005905A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | A mildly alkaline, low-built, solid fabric treatment detergent composition comprising phthalimido peroxy caproic acid |
WO2011005844A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Method of laundering fabric using a compacted laundry detergent composition |
WO2011005623A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Laundry detergent composition comprising low level of bleach |
WO2011005813A1 (en) | 2009-07-09 | 2011-01-13 | The Procter & Gamble Company | Method of laundering fabric using a compacted laundry detergent composition |
WO2011016958A2 (en) | 2009-07-27 | 2011-02-10 | The Procter & Gamble Company | Detergent composition |
WO2011025615A2 (en) | 2009-08-13 | 2011-03-03 | The Procter & Gamble Company | Method of laundering fabrics at low temperature |
WO2011023716A1 (en) | 2009-08-26 | 2011-03-03 | Henkel Ag & Co. Kgaa | Improved washing performance using radical traps |
Non-Patent Citations (1)
Title |
---|
HODGDON, KALER, CURRENT OPINION IN COLLOID & INTERFACE SCIENCE, vol. 12, 2007, pages 121 - 128 |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2874506B1 (en) * | 2012-07-18 | 2019-04-10 | Danisco US Inc. | Method of making enzyme granules |
JP2014047313A (en) * | 2012-09-03 | 2014-03-17 | Pureson Corp | Liquid detergent and method for manufacturing the same |
WO2014115804A1 (en) * | 2013-01-25 | 2014-07-31 | ライオン株式会社 | Enzyme preparation for detergent, liquid detergent, and method for manufacturing same |
WO2016005392A1 (en) * | 2014-07-08 | 2016-01-14 | Novozymes A/S | Co-granulate of enzyme and bleach catalyst |
CN106795464A (en) * | 2014-07-08 | 2017-05-31 | 诺维信公司 | The common particle of enzyme and bleaching catalyst |
CN106795464B (en) * | 2014-07-08 | 2020-02-21 | 诺维信公司 | Co-particles of enzyme and bleach catalyst |
US10543464B2 (en) | 2015-02-10 | 2020-01-28 | Novozymes A/S | Method for mixing of particles |
WO2016177439A1 (en) * | 2015-05-07 | 2016-11-10 | Novozymes A/S | Manganese bleach catalyst / enzyme granules for use in dishwash detergents |
CN107683326A (en) * | 2015-05-07 | 2018-02-09 | 诺维信公司 | Manganese bleaching catalyst/enzyme granulate for dish washing detergent |
CN107683326B (en) * | 2015-05-07 | 2021-10-08 | 诺维信公司 | Manganese bleach catalyst/enzyme particles for dishwashing detergents |
US11021681B2 (en) | 2015-05-07 | 2021-06-01 | Novozymes A/S | Manganese bleach catalyst granules for use in dishwash detergents |
WO2017204788A1 (en) * | 2016-05-24 | 2017-11-30 | Shafer Kim | Composition of probiotics and digestive enzymes and method of preparing and using the same |
WO2018067489A1 (en) * | 2016-10-03 | 2018-04-12 | The Procter & Gamble Company | Low ph laundry detergent composition |
EP3301151A1 (en) * | 2016-10-03 | 2018-04-04 | The Procter & Gamble Company | Low ph laundry detergent composition |
CN109715773A (en) * | 2016-10-03 | 2019-05-03 | 宝洁公司 | The base detergent particle of the spray drying of low pH is generated in cleaning solution |
WO2018067493A1 (en) * | 2016-10-03 | 2018-04-12 | The Procter & Gamble Company | Spray-dried base detergent particle giving rise to a low ph in the wash |
EP3301153A1 (en) * | 2016-10-03 | 2018-04-04 | The Procter & Gamble Company | Process for preparing a spray-dried laundry detergent particle |
RU2716255C1 (en) * | 2016-10-03 | 2020-03-11 | Дзе Проктер Энд Гэмбл Компани | DETERGENT COMPOSITION FOR WASHING WITH LOW pH |
US10676703B2 (en) | 2016-10-03 | 2020-06-09 | The Procter & Gamble Company | Process for preparing a spray-dried laundry detergent particle |
WO2018067494A1 (en) * | 2016-10-03 | 2018-04-12 | The Procter & Gamble Company | Low ph laundry detergent composition |
CN109715773B (en) * | 2016-10-03 | 2021-12-24 | 宝洁公司 | Spray-dried base detergent particles producing low pH in wash liquor |
EP3301152A1 (en) * | 2016-10-03 | 2018-04-04 | The Procter & Gamble Company | Spray-dried base detergent particle giving rise to a low ph in the wash |
WO2021156342A1 (en) | 2020-02-04 | 2021-08-12 | Novozymes A/S | Solid stabilized laccase compositions |
WO2022171872A1 (en) | 2021-02-12 | 2022-08-18 | Novozymes A/S | Stabilized biological detergents |
EP4206309A1 (en) | 2021-12-30 | 2023-07-05 | Novozymes A/S | Protein particles with improved whiteness |
WO2023126254A1 (en) | 2021-12-30 | 2023-07-06 | Novozymes A/S | Protein particles with improved whiteness |
Also Published As
Publication number | Publication date |
---|---|
EP2563910B1 (en) | 2015-09-30 |
MX2012012096A (en) | 2012-12-17 |
ES2646166T3 (en) | 2017-12-12 |
PL2840134T3 (en) | 2018-02-28 |
EP2840134A1 (en) | 2015-02-25 |
KR101904484B1 (en) | 2018-11-30 |
MX349735B (en) | 2017-08-10 |
RU2012150279A (en) | 2014-06-10 |
BR112012024674B1 (en) | 2019-07-02 |
EP2840134B1 (en) | 2017-08-30 |
CN106978403A (en) | 2017-07-25 |
KR20130066612A (en) | 2013-06-20 |
EP2563910A1 (en) | 2013-03-06 |
RU2573907C2 (en) | 2016-01-27 |
JP2013529072A (en) | 2013-07-18 |
AU2011246662B2 (en) | 2014-09-25 |
JP5944887B2 (en) | 2016-07-05 |
EP3279319B1 (en) | 2020-06-10 |
AU2011246662A1 (en) | 2012-10-25 |
CN102906251A (en) | 2013-01-30 |
US9107433B2 (en) | 2015-08-18 |
CN102906251B (en) | 2016-11-16 |
EP3279319A1 (en) | 2018-02-07 |
ZA201207687B (en) | 2013-06-26 |
CA2797032A1 (en) | 2011-11-03 |
CN106978403B (en) | 2021-12-14 |
US20130040872A1 (en) | 2013-02-14 |
BR112012024674A2 (en) | 2016-06-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9107433B2 (en) | Enzyme granules | |
EP2732018B1 (en) | Storage-stable enzyme granules | |
EP2721137B1 (en) | Particulate composition | |
EP3039113B1 (en) | Enzyme granule with fluorescent whitening agent | |
JP2005531308A (en) | Granule stabilization | |
US11753605B2 (en) | Multi-core granules | |
EP4206309A1 (en) | Protein particles with improved whiteness | |
WO2022171872A1 (en) | Stabilized biological detergents | |
US20230193162A1 (en) | Low dusting granules | |
US20200318037A1 (en) | Low dusting granules |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180025872.8 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11715914 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2012/012096 Country of ref document: MX |
|
ENP | Entry into the national phase |
Ref document number: 2797032 Country of ref document: CA |
|
ENP | Entry into the national phase |
Ref document number: 0169012 Country of ref document: KE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13643008 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2013506580 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011715914 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2011246662 Country of ref document: AU Date of ref document: 20110415 Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1201005634 Country of ref document: TH |
|
WWE | Wipo information: entry into national phase |
Ref document number: 9303/CHENP/2012 Country of ref document: IN |
|
ENP | Entry into the national phase |
Ref document number: 20127030043 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2012150279 Country of ref document: RU Kind code of ref document: A |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112012024674 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112012024674 Country of ref document: BR Kind code of ref document: A2 Effective date: 20120927 |